Insecticidal substituted acetate compounds

ABSTRACT

Substituted acetate compounds represented by the formula   &lt;IMAGE&gt; which are useful as pesticides and pesticidal composition containing the substituted acetate compounds as active ingredients, as well as processes for preparing the compounds and the compositions are disclosed.

This is a division of application Ser. No. 378,301, filed July 11, 1973,now U.S. Pat. No. 3,996,244.

SUMMARY OF THE INVENTION

1. Field of the Invention

This invention relates to a pesticide, and more particularly, thisinvention relates to substituted acetate compounds of the followingformula (I) useful for controlling an arthropod, pesticidal compositionscontaining as active ingredients at least one substituted acetatecompound of the formula (I), as well as processes for preparing thesubstituted acetate compounds and the pesticidal compositions.

The substituted acetate compounds of this invention are represented bythe formula: ##STR2## wherein Y represents a substituted aromatic groupor an unsaturated Alicyclic group having an appropriate plane and isselected from the group consisting of the formulae ##STR3## in which R₁and R₂ are individually hydrogen, halogen, cyano, nitro, lower alkyl,lower alkenyl, lower alkynyl, lower alkoxy, lower alkoxyalkyl,halogen-substituted lower alkyl, halogen-substituted lower alkenyl,halogen-substituted lower alkynyl, lower-alkylthio, lower alkylsulfoxyl,acyl, acyloxy, lower alkoxycarbonyl, lower alkenyloxycarbonyl, loweralkynyloxycarbonyl, methylenedioxy, tetramethylene or trimethylenegroup; R₃ and R₄ are individually hydrogen, halogen, cyano, nitro, loweralkyl, lower alkenyl, lower alkynyl, lower alkoxy lower alkoxyalkyl,halogen-substituted lower alkyl, halogen-substituted lower alkenyl,halogen-substituted lower alkynyl, lower alkylthio, lower alkylsulfoxyl,acyl, acyloxy, lower alkoxycarbonyl, lower alkenyloxycarbonyl or loweralkynyloxycarbonyl group; A represents an oxygen atom or a sulfur atom;R₅ represents hydrogen, halogen, cyano, nitro or lower alkyl group; m isan integer of from 1 to 3; R₆ represents hydrogen, halogen, cyano, nitroor lower alkyl group; n is an integer of from 1 to 3; and the dottedline in the formula (V) represents a double bond present at a positionconjugated or non-conjugated with the ketone (C=O), or Y represents asubstituted ethylene group of the formula (VI) ##STR4## in which R₇, R₈and R₉ constitutes a plane together with the double bond at β - γposition of the ester group, and are individually hydrogen, lower alkyl,lower alkenyl, lower alkynyl, halogen, acyl or acyloxy; Z represents astraight or branched lower alkyl, lower alkenyl, lower alkynyl, loweralkoxy, cyano, halogen-substituted lower alkyl, halogen-substitutedlower alkenyl group or an Alicyclic group having 3 to 7 carbon atoms; Xrepresents a group corresponding to an alcohol moiety of the ester-typeinsecticides which are known as pyrethroid insecticides, and is selectedfrom the group consisting of the formulae ##STR5## in which R₁₀represents an allyl, propargyl, benzyl, thenyl, furylmethyl, phenoxy orphenylthio group; R₁₁ represents hydrogen, methyl, trifluoromethyl orhalogen, R₁₀ and R₁₁ may, when they are bonded to each other atterminals, form a trimethylene or tetramethylene group; R₁₂ representshydrogen, ethynyl or cyano; t is an integer of from 1 to 2; B representsan oxygen or sulfur atom or a group --CH=CH--; R₁₃ representsphthalimide, thiophthalimide, di- or tetrahydrophthalimide ordialkylmaleimide; R₁₄ represents allyl, propargyl, benzyl or alkadienyl;R₁₅ represents hydrogen or methyl; R₁₆ represents phenyl, thienyl orfuryl; and W represents methyl or halogen. Preferred ranges of compoundswithin the formula (I) are as follows:

1. compounds of the formula; ##STR6## wherein R₁ is a member selectedfrom the group consisting of hydrogen, methoxy, ethoxy, acetoxy,methylsulfinyl, C₁ -C₄ alkyl, trifluoromethyl, allyl, acetyl,ethoxycarbonyl, methylenedioxy, methylthio, trimethylene,tetramethylene, chlorine, fluorine, iodine, isopropenyl, propargyl,methoxymethyl, ethoxymethyl, chloroethylene, chloroallyl, butyryl,butylthio, allyloxycarbonyl, nitro and methoxycarbonyl; R₂ is a memberselected from the group consisting of hydrogen, methyl, methoxy,chlorine and bromine; R₃ is hydrogen or methyl; Z is a member selectedfrom the group consisting of C₁ -C₄ alkyl, ethoxy, allyl, bromoethyl,cyclohexyl, cyclopropylmethyl, isopropenyl, propargyl, trifluoromethyland cyano; and X is a member selected from the group consisting of:##STR7##

2. compounds of the formula; ##STR8## wherein R₃ is a member selectedfrom the group consisting of hydrogen, methyl, allyl, methoxycarbonyland acetyl; R₄ is hydrogen; Z is a member selected from the groupconsisting of ethyl, propyl and allyl; and X is a member selected fromthe group consisting of ##STR9##

3. compounds of the formula; ##STR10## wherein R₃ is a member selectedfrom the group consisting of hydrogen, methyl, allyl, methoxycarbonyland butyryl; R₄ is hydrogen; Z is ethyl or propyl; X is a memberselected from the group consisting of

4. compounds of the formula; ##STR11## wherein R₇ is a member selectedfrom the group consisting of hydrogen, methyl and ethyl; R₈ is hydrogenor methyl; R₉ is methyl; Z is C₁ -C₃ alkyl; and X is a member selectedfrom the group consisting of ##STR12##

5. compounds of the formula; ##STR13## wherein R₅ is hydrogen or methyl;m is an integer of 1 or 2; Z is a member selected from the groupconsisting of methyl, propyl, allyl and propargyl; X is a memberselected from the group consisting of ##STR14##

6. compounds of the formula; ##STR15## wherein R₆ is methyl, n is aninteger of 1, Z is ethyl or propyl; X is a member selected from thegroup consisting of ##STR16##

Among the present compounds, the phenylacetic acid esters prepared byreacting phenylacetic acid derivatives of the formula; ##STR17## whereinR₁ represents a straight or branched chain alkyl group having 1 to 5carbon atoms, a straight or branched chain alkoxy group having 1 to 5carbon atoms, a halogen atom or a thiomethyl group and two of R₁ mayform a trimethylene --(CH₂)₃ -- or tetramethylene --(CH₂)₄ -- or amethylenedioxy group --O--CH₂ --O--; n' is an integer of from 1 to 4;and R₂ represents a straight or branched alkyl group having 3 to 5carbon atoms, allyl group, a propargyl group or isopropenyl group; witha pyrethroid alcohol have a prominent effects to injurious insects andlow toxicity to mammals. And, therefore, the above mentionedphenylacetic acids are important as intermediate of the presentinvention.

2. Description of the Prior Art

Since BHC and DDT have been developed, remarkable advances have beenmade in the organic agricultural agents such as phosphorus agents,carbamates, pyrethroids and the progress of such organic agriculturalagents now establishes a certain close correlation between the consumedquantity of pesticides and the harvested quantity of crops. However, onthe other hand, these agricultural agents have caused pollutions by theenvironment contamination and at present there are many problems such asthe accumulation of toxicity and the chronic toxicity as well as thegeneration of a wide variety of pesticide-resistant noxious insects. Thedesirable requirements for pesticides are, therefore, that the activepesticides exhibit a low toxicity, a low residual and a rapiddecomposition and they are converted into non-toxic materials uponentrance into one of the biological cycles of the ecological system. Inparticular, the compounds containing no heavy metals nor halogen atomsand composed mainly of carbon, hydrogen and oxygen are considered to beadvantageous as agricultural agents.

The active groups of the pesticides presently used include organicphosphorus compounds, carbamates, chrysanthemic acid esters,organochloric compounds, etc., and most of the researchers in this fieldnow endeavour to develop new types of pesticides by considering thesuperiority or inferiority of each of the above active groups andscreening various synthetic derivatives retaining only the superiorityof the known pesticides.

The present inventors considered that each of the above well-knownactive groups has certain properties as basic pesticidal characteristicsinherent to the specific active group and that the disadvantagesassociated with the specific active group would not be eliminated unlessdeparting from the above specific properties. As a result of extensiveresearches for active groups having novel chemical structures, thepresent inventors found the new and useful acetic acid estersrepresented by the above formula (I).

The compounds of this invention have various advantages broadly and alsoexhibit strong selectivity, and the chemical structures retaining onlyproperties advantageous as agricultural agents can be considereddepending upon the specific type of the compounds of this invention.

Hithertofore, esters which are considered to be pesticidal activegroups, for example, phosphoric acid esters and chrysanthemic acidesters are believed to have their activities in the basic structures ofphosphoric acid and cyclopropanecarboxylic acid, respectively. Theseesters contain a S (or O) atom bonded to a pentavalent phosphorus by adouble bond as an essential structure of the phosphoric acid esters anda three-membered ring as an essential structure of the chrysanthemicacid esters, respectively, and the pesticidal activity tends to bestrengthened or weakened depending upon the type of moieties presentaround the above essential structure as a nucleus.

In the compounds of this invention, the acid moiety represented by theformula (XI) ##STR18## is considered to be an important active basicstructure, and its essential structure is completed by a hydrogen atomat α-position of the ester group, an appropriate substituent (Z) and asubstituent (Y) which are characterized in its plane structure. On theother hand, the alcohol moiety of the ester corresponds to the alcoholmoiety of the well-known chrysanthemic acid esters as shown by theexamples of compounds described below, but, in accordance with thepresent invention, it was found that highly active pesticides can beprepared by esterification of the acids represented by the formula (XI)with the above alcohol moiety and that the compounds having asurprisingly high selectivity can be prepared by using an appropriatecombination of an acid moiety and an alcohol moiety. However, the orderof activity of the ester composed of the known alcohol and the knownacid cannot be applied as it is to the evaluation of the activity of theesters in accordance with the present invention since the esters of thisinvention exhibit activities entirely different those of the knownesters. Accordingly, the esters composed of the acid used in the presentinvention and the alcohol which has been found to form a highly activeester in the known pesticides do not necessarily exhibit an excellentactivity.

In addition, in accordance with the present invention, variousadvantages such as immediate onset of action, permeability, transferinto living plants, residual activity, pesticidal activity,metamorphosis disturbance, sterilization, prohibition of egg-lying canfreely be controlled by appropriately selecting a combination of an acidof the present invention and a wide variety of alcohols. Also, withrespect to the spectrum of pesticidal activity, the compounds of thisinvention exhibit a selective or non-selective activity on such order asCoreoptera, Lepidoptera, Diptera, Orthoptera, Hemiptera, Homoptera andAcarus depending upon a specific combination of acid and an alcoholaccording to the present invention. Further, the compounds of thisinvention are expected to be useful for controlling noxious insects suchas a nematoda. Other important features of the compounds of thisinvention are that they are active against noxious insects which areresistant to the pesticides presently used because of their basicstructures different from these of the known pesticides to which theinsects are resistant, and that they are totally low toxic to mammalsincluding man as indicated by Experiments shown below.

As the results of the present invention, the substituted acetatecompounds of the formula, ##STR19## wherein R'₁ represents straight orbranched chain alkyl having 1 to 4 carbon atoms, halogen or alkoxyhaving 1 to 4 carbon atoms; R'₂ represents hydrogen or a group whichcompletes, together with R'₁, methylenedioxy; and X' represents a groupof the formula, ##STR20## are more excellent in insecticidal effect, akilling effect and a knock down effect than the other substitutedacetate compounds of the formula (I).

In order to make the above fact clearer, the superiority of thecompounds represented by the formula (I') in biological effects is shownbelow with reference to Experimental Examples. But the other compoundsof the formula (I) and their geometrical isomers and optical isomersdisplay more excellent effects as well than the known insecticidalagents.

In preparing the substituted acetic acid esters represented by theformula (I), an acid represented by the formula ##STR21## wherein Y andZ are as defined above, or a reactive derivative thereof is reacted withan alcohol represented by the formula

    X -- OH                                                    (XII)

wherein X is as defined above, or a halide or sulfoxylate thereof.

The term "reactive derivative" of the acid used herein refers to an acidhalide, an acid anhydride, an ester with an alcohol having a low boilingpoint, and an alkali metal salt, a silver salt or an organic tertiarybase salt of the acid.

The substituted acetic acid esters represented by the formula (I)include optical isomers due to the carbon atom at α-position, and it isto be understood that the present invention is contemplated to includesuch optical isomers.

In carrying out the production of the substituted acetic acid esters ofthe formula (I), the esterification between the acid (XI) and thealcohol (XII) can advantageously be accomplished by reacting thereactants in an appropriate inert solvent at room temperature or anelevated temperature under an appropriate dehydrating condition, e.g.,in the presence of cyclohexylcarbodiimide. When an acid halide is usedas a reactive derivative of the acid (XI), the desired ester can beobtained in high yield by reacting the alcohol (XII) and the acid halideat room temperature using an acid acceptor, for example, an organictertiary amine such as pyridine, triethylamine and the like. The acidhalides which can be used in the process of this invention may be anytype of halides within the scope of this invention, but an acid chlorideis generally preferred. The presence of an inert solvent is notessential in the esterification reaction, but it is generally preferredto use a solvent in order to assure a smooth reaction. Any solvent whichis inert to the reactants and the ester product may be used and apreferred inert solvent includes benzene, toluene and petroleum benzine.When an ester of the acid (XI) and a low boiling point alcohol, e.g.,methanol, ethanol and the like is used as a reactive derivative of theacid, the desired ester (I) can be obtained in high yield byheat-reacting the ester and the alcohol (XII) with heating in thepresence of an appropriate organic base catalyst, preferably, an alkalimetal alkoxide corresponding to the low boiling alcohol of the esterused or sodium hydride in an inert solvent such as toluene whileremoving a low boiling alcohol liberated during the reaction from thereaction system by a fractional distillation column.

In an alternative esterification procedure using an acid anhydride as areactive derivative of the acid (XI), the desired ester can be obtainedby reacting the acid anhydride with the alcohol (XII) at roomtemperature without using specific reaction aids. In this case, it ispreferred to heat the reaction system and to use a solvent such astoluene, xylene and the like in order to ensure a smooth reaction, butthe heating and the use of solvent are not critical in this procedure.

When a halide or sulfoxylate of the above alcohol (XII) is used, theacid (XI) is generally employed in the form of an alkali metal salt, asilver salt or an organic tertiary base salt. These salts may be formedin situ by adding simultaneously the acid (XII) and the correspondingbase to the reaction system. In this case, a solvent such as benzene,acetone, dimethylformamide and the like is preferably used, and thereaction is preferably conducted by heating the reaction system at orbelow the boiling point of the solvent used. A preferred halogen for thehalide of alcohol (XII) includes chlorine and bromine.

Representative examples of the compounds of this invention areillustrated below, but the present invention is not limited thereto.

    __________________________________________________________________________    Compound                                                                      No.                                                                           __________________________________________________________________________           ##STR22##                                                                    5'-Benzyl-3'-furylmethyl-α-ethyl-phenylacetate                          n.sub.D.sup.17 1.5545                                                          ##STR23##                                                                    3'-Phenoxybenzyl-α-ethylphenylacetate                                   n.sub.D.sup.22 1.5712                                                          ##STR24##                                                                    3'-Phenoxybenzyl-α-ethoxyphenylacetate                                  n.sub.D.sup.24 1.5275                                                          ##STR25##                                                                    3',4',5',6'-Tetrahydrophthalimidomethyl-α-ethyl-                        phenylacetate                                                                 n.sub.D.sup.22 1.5403                                                          ##STR26##                                                                    Dimethylmaleimidomethyl-α-allylphenylacetate                            n.sub.D.sup.22 1.5349                                                          ##STR27##                                                                    5'-Propargylfurfuryl-α-ethyl-2-thienylacetate                           n.sub.D.sup.22 1.5835                                                          ##STR28##                                                                    3',4',5',6'-Tetrahydrophthalimidomethyl-2-(3"-                                methyl-2"-cyclopentene-1"-yl)-propionate                                      n.sub.D.sup.23 1.5648                                                          ##STR29##                                                                    5'-Propargyl-α '-ethynyl-3'-furylmethyl-α-ethyl-                  phenylacetate                                                                 n.sub.D.sup.24.5 1.5310                                                        ##STR30##                                                                    5'-Benzyl-3'-furylmethyl-2-(3"-methyl-2"-cyclo-                               pentenone-2"-yl)-butyrate                                                     n.sub.D.sup.22 1.5123                                                   10.                                                                                  ##STR31##                                                                    4'-Propargylbenzyl-α-ethylphenylacetate                                 n.sub.D.sup.23 1.5039                                                          ##STR32##                                                                    5'-(1',2',3',4'-Tetrahydronaphthalenyl)-methyl-α-                       methylphenylacetate                                                           n.sub.D.sup.24 1.5536                                                          ##STR33##                                                                    5'-Benzyl-3'-thenyl-α-ethylphenylacetate                                n.sub.D.sup.22 1.5488                                                          ##STR34##                                                                    5'-Benzyl-3'-thenyl-α-isopropyl-phenylacetate                           n.sub.D.sup.22 1.5613                                                          ##STR35##                                                                    3'-Phenoxy-α'-cyanobenzyl-α-ethylphenylacetate                    n.sub.D.sup.21 1.5638                                                          ##STR36##                                                                    5'-Benzyl-3'-furylmethyl-α-(2"-bromoethyl)-                             phenylacetate                                                                 n.sub.D.sup.23 1.5911                                                          ##STR37##                                                                    2'-Allyl-3'-methyl-2'-cyclopentene-1'-one-4"-yl-α-                      ethyl-2-furylacetate                                                          n.sub.D.sup.22 1.5118                                                          ##STR38##                                                                    5-Benzyl-3'-furylmethyl-α-cyclohexyl-phenylacetate                      m.p. 51 - 53° C                                                         ##STR39##                                                                    5'-Benzyl-3'-furylmethyl-2-ethyl-3,4-dimethyl-3-                              pentenoate                                                                    n.sub.D.sup.23 1.5417                                                          ##STR40##                                                                    5'-Propargyl-2'-methyl-3'-furylmethyl-α-                                cyclopropylmethylphenylacetate                                                n.sub.D.sup.24 1.5632                                                   20.                                                                                  ##STR41##                                                                    5'-Propargylfurfuryl-α-allyl-2-thenylacetate                            n.sub.D.sup.22 1.5274                                                          ##STR42##                                                                    5'-Benzyl-3'-furylmethyl-2-methyl-3-ethyl-3-                                  (cis,trans)-pentenoate                                                        n.sub.D.sup.21 1.5693                                                          ##STR43##                                                                    5'-Benzyl-3'-furylmethyl-α-isopropyl-4-methoxy-                         phenylacetate                                                                 n.sub.D.sup.17 1.5470                                                          ##STR44##                                                                    5'-Benzyl-3'-furylmethyl-α-ethyl-3-methoxyphenyl-                       acetate                                                                       n.sub.D.sup.25 1.5481                                                          ##STR45##                                                                    3'-Phenoxybenzyl-α-isopropyl-3,4-dimethoxyphenyl-                       acetate                                                                       n.sub.D.sup.25 1.5655                                                          ##STR46##                                                                    3'-Phenoxybenzyl-α-ethyl-4-acetoxyphenylacetate                         n.sub.D.sup.25 1.5621                                                          ##STR47##                                                                    5'-Benzyl-3'-furylmethyl-α-ethyl-4-methylsulfoxy-                       phenylacetate                                                                 n.sub.D.sup.25 1.5448                                                          ##STR48##                                                                    3',4',5',6'-Tetrahydrophthalimidomethyl-2-ethyl-                              2,4,6-trimethylphenylacetate                                                  n.sub.D.sup.25 1.5399                                                          ##STR49##                                                                    5'-Propargyl-2'-methyl-3'-furylmethyl-α-isopropyl-                      4-trifluoromethylphenylacetate                                                n.sub.D.sup.25 1.5368                                                          ##STR50##                                                                    5'-Benzyl-3'-furylmethyl-α-isopropyl-4-allylphenyl-                     acetate                                                                       n.sub.D.sup.25 1.5277                                                   30.                                                                                  ##STR51##                                                                    2'-Allyl-3'-methyl-2'-cyclopentene-1-one-4-yl-                                α-allyl-p-acetylphenylacetate                                           n.sub.D.sup.25 1.5566                                                          ##STR52##                                                                    5'-Propargylfurfuryl-α-isopropyl-4-carbethoxy-                          phenylacetate                                                                 n.sub.D.sup.25 1.5711                                                          ##STR53##                                                                    3'-Phenoxybenzyl-α-isopropenyl-3,4-methylenedioxy-                      phenylacetate                                                                 n.sub.D.sup.25 1.5325                                                          ##STR54##                                                                    3'-Phenoxybenzyl-α-isopropyl-5-carbomethoxy-2-                          furylacetate                                                                  n.sub.D.sup.25 1.5367                                                          ##STR55##                                                                    3'-Phenoxy-α '-cyanobenzyl-α-isopropyl-4-ethoxy-                  phenylacetate                                                                 n.sub.D.sup.25 1.5208                                                          ##STR56##                                                                    5'-Benzyl-3'-furylmethyl-α-isopropyl-4-methyl-                          thiophenylacetate                                                             n.sub.D.sup.25 1.5335                                                          ##STR57##                                                                    5'-Benzyl-3'-furylmethyl-α-isopropyl-1,2,3,4-                           tetrahydronaphthalene-6-yl-acetate                                            n.sub.D.sup.21 1.3689                                                          ##STR58##                                                                    5'-Propargyl-2'-(α '-ethynyl)-furylmethyl-α-                      isopropyl-3,4-methylenedioxyphenylacetate                                     n.sub.D.sup.21 1.5236                                                          ##STR59##                                                                    3'-Phenoxybenzyl-α-t-butyl-4-trifluoromethylphenyl-                     acetate                                                                       n.sub.D.sup.25 1.5671                                                          ##STR60##                                                                    5'-Benzyl-3'-furylmethyl-α-trifluoromethyl-4-                           methoxyphenylacetate                                                          n.sub.D.sup.25 1.5474                                                   40.                                                                                  ##STR61##                                                                    Dimethylmaleimidomethyl-α-isopropyl-3,5-dichloro-                       4-methylphenylacetate                                                         n.sub.D.sup.25 1.5239                                                          ##STR62##                                                                    2'-Allyl-3'-methyl-2'-cyclopentene-1'-one-4'-yl-                              α-isopropyl-5-indanylacetate                                            n.sub.D.sup.25 1.5753                                                          ##STR63##                                                                    4'-Phenyl-3'-chloro-2'-butene-1'-yl-α-isopropyl-                        4-isopropenylphenylacetate                                                    n.sub.D.sup.25 1.5878                                                          ##STR64##                                                                    3'-Phenoxybenzyl-α-isopropyl-5-(1,2,3,4-tetrahydro)-                    naphthalenylacetate                                                           n.sub.D.sup.20 1.5660                                                          ##STR65##                                                                    3' -Benzylbenzyl-α-cyano-2-methoxyphenylacetate                         n.sub.D.sup.23 1.5702                                                          ##STR66##                                                                    3'-Phenoxybenzyl-α-ethyl-4-propargylphenylacetate                       n.sub.D.sup.25 1.5513                                                          ##STR67##                                                                    5'-Propargyl-2'-thenyl-α-isopropenyl-3-methoxy-4-                       methylphenylacetate                                                           n.sub.D.sup.20 1.5466                                                          ##STR68##                                                                    5'-Phenoxyfurfuryl-α-isopropyl-4-methoxymethyl-                         phenylacetate                                                                 n.sub.D.sup.25 1.5738                                                          ##STR69##                                                                    Phthalimidomethyl-α-isopropyl-4-ethoxymethyl-                           phenylacetate                                                                 n.sub.D.sup.25 1.5221                                                          ##STR70##                                                                    2',6'-Dimethyl-4'-allylbenzyl-α-isopropyl-4-1"-                         chloroethylene-1"-yl-phenylacetate                                            n.sub.D.sup.25 1.5413                                                   50.                                                                                  ##STR71##                                                                    4',5'-Tetramethylene-2-thenyl-α-isopropyl-4-(2"-                        chloroallyl)-phenylacetate                                                    n.sub.D.sup.25 1.5239                                                          ##STR72##                                                                    5'-Propargyl-2'-(α'-ethynyl)-furfuryl-α-isopropyl-                4-methoxyphenylacetate                                                        n.sub.D.sup.26 1.5253                                                          ##STR73##                                                                    5'-Propargyl-2'-thenyl-α-ethyl-4-isobutyrylphenyl-                      acetate                                                                       n.sub.D.sup.25 1.5549                                                          ##STR74##                                                                    2'-Benzyl-2'-cyclopentene-1'-one-4'-yl-α-ethyl-                         3-butylthio-phenylacetate                                                     n.sub.D.sup.25 1.5508                                                          ##STR75##                                                                    4'-Propargylbenzyl-α-isopropyl-5-acetyl-3-thienyl-                      acetate                                                                       n.sub.D.sup.22 1.5259                                                          ##STR76##                                                                    Monothiophthalimidomethyl-α-allyl-3,4-dimethoxy-                        phenylacetate                                                                 n.sub.D.sup.19 1.5350                                                          ##STR77##                                                                    5'-(2"-Thenyl)-3'-furylmethyl-α-isopropyl-3-(5-                         isobutyryl)-furylacetate                                                      n.sub.D.sup.22 1.5324                                                          ##STR78##                                                                    5'-Benzyl-3'-thenyl-α-isopropyl-3-carballyloxy-                         phenylacetate                                                                 n.sub.D.sup.25 1.5556                                                          ##STR79##                                                                    3',4'-Dichloro-α'-ethynylbenzyl-α-isopropyl-4-                    methoxyphenylacetate                                                          n.sub.D.sup.25 1.5368                                                          ##STR80##                                                                    5'-Propargyl-2'-thenyl-α-isopropyl-3-methoxyphenyl-                     acetate                                                                       n.sub.D.sup.25 1.5552                                                   60.                                                                                  ##STR81##                                                                    3'-Benzylbenzyl-α-isopropyl-3-methoxy-4-methyl-                         phenylacetate                                                                 n.sub.D.sup.25 1.5509                                                          ##STR82##                                                                    5'-Phenoxyfurfuryl-α-isopropyl-2-methyl-4-methoxy-                      phenylacetate                                                                 n.sub.D.sup.25 1.5501                                                          ##STR83##                                                                    3'-Phenoxybenzyl-α-isopropyl-4-methoxyphenylacetate                     n.sub.D.sup.19 1.5878                                                          ##STR84##                                                                    5'-Phenoxyfurfuryl-α-isopropyl-4-methoxyphenyl-                         acetate                                                                       n.sub.D.sup.19 1.5878                                                          ##STR85##                                                                    5'-Phenylthio-3'-furylmethyl-α-isopropyl-4-                             methoxyphenylacetate                                                          n.sub.D.sup.16 1.5371                                                          ##STR86##                                                                    Dimethylmaleimidomethyl-α-isopropenyl-4-tri-                            fluoromethylphenylacetate                                                     n.sub.D.sup.25 1.5779                                                          ##STR87##                                                                    5'-Benzyl-3'-furylmethyl-α-ethyl-3-trifluoromethyl-                     phenylacetate                                                                 n.sub.D.sup.25 1.5647                                                          ##STR88##                                                                    2'-Propargyl-3'-methyl-2'-cyclopentene-1' -one-                               4'-yl-d-isopropyl-3-methoxyphenylacetate                                      n.sub.D.sup.25 1.5628                                                          ##STR89##                                                                    3'-Phenoxybenzyl-α-ethyl-2,4,6-trimethyl-3-nitro-                       phenylacetate                                                                 n.sub.D.sup.25 1.5971                                                          ##STR90##                                                                    3'-Trifluoromethyl-α'-ethynylbenzyl-α-ethyl-4-                    methoxyphenylacetate                                                          n.sub.D.sup.25 1.5119                                                   70.                                                                                  ##STR91##                                                                    5'-Benzyl-3'-thenylmethyl-α-isopropyl-2-methyl-3-                       isopropenylphenylacetate                                                      n.sub.D.sup.25 1.5299                                                          ##STR92##                                                                    5'-Benzyl-3'-furylmethyl-α-propargyl-3-methoxy-                         phenylacetate                                                                 n.sub.D.sup.25 1.5478                                                          ##STR93##                                                                    5'-Benzyl-3'-furylmethyl-α-isopropyl-3-nitro-4,5-                       dimethylphenylacetate                                                         n.sub.D.sup.25 1.5371                                                          ##STR94##                                                                    3',4',5',6'-Tetrahydrophthalimidomethyl-α-isopropyl-                    p-methoxyphenylacetate                                                        n.sub.D.sup.25 1.5365                                                          ##STR95##                                                                    5'-Propargylfurfuryl-α-isopropyl-4-carbomethoxy-                        phenylacetate                                                                 n.sub.D.sup.25 1.5335                                                          ##STR96##                                                                    5'-Benzyl-3'-furylmethyl-α-isopropyl-4-carbomethoxy-                    phenylacetate                                                                 n.sub.D.sup.24 1.5640                                                          ##STR97##                                                                    5'-Benzyl-3'-furylmethyl-α-isopropyl-3,4-dimethoxy-                     phenylacetate                                                                 n.sub.D.sup.25 1.5456                                                          ##STR98##                                                                    3'-Phenoxybenzyl-α-isopropyl-5-carbethoxy-2-                            thenylacetate                                                                 n.sub.D.sup.25 1.5777                                                          ##STR99##                                                                    5'-Benzyl-3'-furylmethyl-α-ethyl-4-allyl-2-thenyl-                      acetate                                                                       n.sub.D.sup.25 1.5510                                                          ##STR100##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropyl-4-allyl-2                          furylacetate                                                                  n.sub.D.sup.25 1.5356                                                   80.                                                                                  ##STR101##                                                                   3'-Phenoxybenzyl-α-ethyl-4-methoxyphenylacetate                         n.sub.D.sup.19 1.5671                                                          ##STR102##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropyl-3-methoxy-                         phenylacetate                                                                 n.sub.D.sup.16 1.5411                                                          ##STR103##                                                                   3'-Phenoxybenzyl-α-isopropenyl-4-methoxyphenylacetate                   n.sub.D.sup.16 1.5798                                                          ##STR104##                                                                   3'-Phenoxybenzyl-α-isopropenyl-3-methoxyphenylacetate                   n.sub.D.sup.18 1.5687                                                          ##STR105##                                                                   3'-Phenoxybenzyl-α-isopropenyl-3,4-dimethoxyphenyl-                     acetate                                                                       n.sub.D.sup.20 1.5713                                                          ##STR106##                                                                   3'-Phenoxybenzyl-α-isopropenyl-3,4-methylenedioxy-                      phenylacetate                                                                 n.sub.D.sup.20 1.5535                                                          ##STR107##                                                                   5'-Benzyl-2'-thenylmethyl-α-isopropyl-4-methoxy-                        phenylacetate                                                                 n.sub.D.sup.20 1.5571                                                          ##STR108##                                                                   3'-Phenoxybenzyl-α-isopropyl-3-methoxypenylacetate                      n.sub.D.sup.17 1.5377                                                          ##STR109##                                                                   4',5'-Tetramethylenefurfuryl-α-isopropyl-4-methoxy-                     phenylacetate                                                                 n.sub.D.sup.19 1.5467                                                          ##STR110##                                                                   3'-Benzylbenzyl-α-isopropyl-4-methoxyphenylacetate                      n.sub.D.sup.20 1.5313                                                   90.                                                                                  ##STR111##                                                                   3',4',5',6'-Tetrahydrophthalimidomethyl-α-iso-                          propenyl-4-methoxyphenylacetate                                               n.sub.D.sup.21 1.5211                                                          ##STR112##                                                                   3'-Phenoxybenzyl-α-isopropyl-4-carbomethoxyphenyl-                      acetate                                                                       n.sub.D.sup.20 1.5413                                                          ##STR113##                                                                   3'-Benzylbenzyl-α-isopropenyl-4-methoxyphenylacetate                    n.sub.D.sup.19 1.5339                                                          ##STR114##                                                                   2'-Allyl-3'-methyl-2'-cyclopentene-1'-one-4-                                  α-ethyl-3-methoxyphenylacetate                                          n.sub.D.sup.19 1.5211                                                          ##STR115##                                                                   5'-Propargyl-α'-ethynylfurfuryl-α-ethyl-4-methoxy-                phenylacetate                                                                 n.sub.D.sup.20 1.5467                                                          ##STR116##                                                                   5'-Propargyl-α'-ethynylfurfuryl-α-isopropyl-4-                    methylthiophenylacetate                                                       n.sub.D.sup.20 1.5518                                                          ##STR117##                                                                   3'-Phenoxybenzyl-α-isopropenyl-2-methyl-4-methoxy-                      phenylacetate                                                                 n.sub.D.sup.20 1.5396                                                          ##STR118##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropyl-3-ethoxy-4-                        bromophenylacetate                                                            n.sub.D.sup.20 1.5218                                                          ##STR119##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropyl-3-chloro-4-                        methoxyphenylacetate                                                          n.sub.D.sup.20 1.5416                                                          ##STR120##                                                                   3'-Phenoxybenzyl-α-isopropyl-3-chloro-4-methoxy-                        phenylacetate                                                                 n.sub.D.sup.20 1.5467                                                   100.                                                                                 ##STR121##                                                                   3'-Phenoxybenzyl-α-isopropenyl-3-chloro-4-methoxy-                      phenylacetate                                                                 n.sub.D.sup.20 1.5331                                                   101.                                                                                 ##STR122##                                                                   3'-Phenoxybenzyl-α-isopropyl-2-chloro-4-methoxy-                        phenylacetate                                                                 n.sub.D.sup.20  1.5476                                                  102.                                                                                 ##STR123##                                                                   5'-Benzyl-3'-furylmethyl-α-ethyl-4-methylphenyl-                        acetate                                                                       n.sub.D.sup.25 1.5474                                                   103.                                                                                 ##STR124##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropyl-4-methyl-                          phenylacetate                                                                 n.sub.D.sup.25 1.5433                                                   104.                                                                                 ##STR125##                                                                   5'-Benzyl-3'-furylmethyl-α-ethyl-3-methylphenyl-                        acetate                                                                       n.sub.D.sup.25 1.5470                                                   105.                                                                                 ##STR126##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropyl-3-methyl-                          phenylacetate                                                                 n.sub.D.sup.25.5 1.5430                                                 106.                                                                                 ##STR127##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropyl-3,4-dimethyl-                      phenylacetate                                                                 n.sub.D.sup.25.5 1.5238                                                 107.                                                                                 ##STR128##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropyl-4-chloro-                          phenylacetate                                                                 n.sub.D.sup.25.5 1.5241                                                 108.                                                                                 ##STR129##                                                                   3'-Phenoxybenzyl-α-isopropyl-4-methylphenylacetate                      n.sub.D.sup.28.5 1.5596                                                 109.                                                                                 ##STR130##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropyl-2-methyl-                          phenylacetate                                                                 n.sub.D.sup.26.5 1.5431                                                 110.                                                                                 ##STR131##                                                                   5'-Benzyl-3'-furylmethyl-α-ethyl-2-methylphenyl-                        acetate                                                                       n.sub.D.sup.26.5 1.5501                                                 111.                                                                                 ##STR132##                                                                   3'-Phenoxybenzyl-α-isopropenyl-4-bromophenylacetate                     n.sub.D.sup.20 1.5278                                                   112.                                                                                 ##STR133##                                                                   5'-Benzyl-2'-thenyl-α-isopropenyl-4-methylphenyl-                       acetate                                                                       n.sub.D.sup.20 1.5439                                                   113.                                                                                 ##STR134##                                                                   5'-Furfuryl-3'-furylmethyl-α-isopropenyl-4-methyl-                      phenylacetate                                                                 n.sub.D.sup.20  1.5411                                                  114.                                                                                 ##STR135##                                                                   5'-Benzyl-2'-methyl-3'-furylmethyl-α-isopropenyl-4-                     chlorophenylacetate                                                           n.sub.D.sup.25 1.5212                                                   115.                                                                                 ##STR136##                                                                   5'-Phenoxy-3'-furylmethyl-α-isopropenyl-4-methyl                        phenylacetate                                                                 n.sub.D.sup.25 1.5471                                                   116.                                                                                 ##STR137##                                                                   3'-Phenoxybenzyl-α-isopropenyl-4-isopropylphenyl-                       acetate                                                                       n.sub.D.sup.20 1.5218                                                   117.                                                                                 ##STR138##                                                                   3'-Phenoxybenzyl-α-isopropenyl-4-isobutylphenyl-                        acetate                                                                       n.sub.D.sup.20 1.5236                                                   118.                                                                                 ##STR139##                                                                   3'-Phenoxybenzyl-α-isopropenyl-4-t-butylphenyl-                         acetate                                                                       n.sub.D.sup.20 1.5311                                                   119.                                                                                 ##STR140##                                                                   3'-Phenoxybenzyl-α-isopropenyl-4-chlorophenylacetate                    n.sub.D.sup.21 1.5322                                                   120.                                                                                 ##STR141##                                                                   3'-Phenoxybenzyl-α-isopropenyl-3-chlorophenylacetate                    n.sub.D.sup.21 1.5393                                                   121.                                                                                 ##STR142##                                                                   3'-Phenoxybenzyl-α-isopropenyl-4-fluorophenylacetate                    n.sub.D.sup.20 1.5363                                                   122.                                                                                 ##STR143##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropenyl-4-isopropyl-                     phenylacetate                                                                 n.sub.D.sup.19 1.5428                                                   123.                                                                                 ##STR144##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropenyl-3-chloro-                        phenylacetate                                                                 n.sub.D.sup.17 1.5411                                                   124.                                                                                 ##STR145##                                                                   3'-Phenoxybenzyl-α-isopropenyl-phenylacetate                            n.sub.D.sup.20 1.5396                                                   125.                                                                                 ##STR146##                                                                   3'-Phenoxybenzyl-α -isopropenyl-4-methylphenylacetate                   n.sub.D.sup.20 1.5378                                                   126.                                                                                 ##STR147##                                                                   3'-Phenoxybenzyl-α-isopropenyl-4-ethylphenylacetate                     n.sub.D.sup.20 1.5441                                                   127.                                                                                 ##STR148##                                                                   3'-Phenoxybenzyl-α-isopropenyl-4-n-propyl-phenyl                        acetate                                                                       n.sub.D.sup.20 1.5466                                                   128.                                                                                 ##STR149##                                                                   5'-Benzyl-3'-furylmethyl-α-isopropenyl-4-methyl-                        phenylacetate                                                                 n.sub.D.sup.20 1.5398                                                   __________________________________________________________________________

The process for preparing the esters in accordance with the presentinvention is illustrated by the following Preparations, but the presentinvention is not limited thereto.

PREPARATION 1 Preparation of 5'-benzyl-3'-furylmethyl-α-ethylphenylacetate (Compound No. 1)

6.20 g (0.02 mole) of α-ethylphenylacetic anhydride and 3.76 g (0.02mole) of 5-benzyl-3-furylmethylalcohol were dissolved in 50 ml of drypyridine and the mixture was stirred at room temperature for 2 hours.The resulting reaction mixture was poured into 100 g of ice water andextracted with three 20 ml portions of ethyl ether. The combined etherlayer was then extracted with two 20 ml portions of 5% aqueous sodiumhydroxide to remove α-ethylphenylacetic acid as a by-product. The etherlayer was washed successively with 10% hydrochloric acid, saturatedaqueous sodium bicarbonate and saturated sodium chloride, drier overanhydrous sodium sulfate, and the ether was removed under reducedpressure to obtain 6.25 g of crude ester as a pale yellow oilysubstance. The resulting oily substance was then purified by columnchromatography using 120 g of activated alumina and a developing solventof benzene-n-hexane (1:3) to obtain 5.68 g (85% theoretical yield) ofthe desired ester as a colorless oily substance.

n_(D) ¹⁷ 1.5545

ν_(max). film 3005, 1724, 1550, 1407, 1180, 806 cm.sup.⁻¹

δ_(ppm) CCl- 7.16 (S. 5H), 7.15 (S. 5H), 7.2 (1H), 5.79 (bs. 1H), 4.78(S. 2H), 3.78 (S. 2H), 3.31 (t. 1H, J=7Hz), 1.3 - 2.3 (m. 2H), 0.83 (t.3H, J=7Hz)

PREPARATION 2 Preparation of m-phenoxybenzyl-α-ethylphenylacetate(Compound No. 2)

2.00 g (0.01 mole) of m-phenoxybenzyl alcohol and 1.19 g (0.015 mole) ofdry pyridine were dissolved in 20 ml of benzene, and 1.83 g (0.01 mole)of α-ethylphenylacetyl chloride dissolved in 5 ml of dry benzene wasadded dropwise thereto under ice-cooling. After completion of addition,the mixture was stirred at room temperature for 3 hours to complete thereaction, and the reaction mixture was poured into 30 g of ice-water.The mixture was separated, and the aqueous layer was extracted with two10 ml portions of benzene. The combined benzene layer was washedsuccessively with 5% hydrochloric acid, saturated aqueous sodiumbicarbonate and saturated aqueous sodium chloride, and benzene wasremoved under reduced pressure. The resulting crude ester was chargedonto a column packed with 40 g of activated alumina using a mixture ofbenzene-n-hexane (1:3) as an eluent to obtain 3.15 g (91% theoreticalyield) of the purified ester.

n_(D) ²² 1.5712

ν_(max).^(film) 3030, 1740, 1590, 1470, 1260, 1220, 1160 cm.sup.⁻¹

δ_(ppm) ^(CCl) 4 7.4 - 5.8 (m. 14H), 4.95 (S. 2H), 3.48 (T. 1H, J=8Hz),2.3 - 1.1 (m. 2H), 0.85 (t. 3H, J=8Hz)

PREPARATION 17 Preparation of5'-benzyl-3'-furylmethyl-α-cyclohexylphenylacetate (Compound No. 17)

2.82 g (0.015 mole) of 5-benzyl-3-furylmethyl alcohol and 2.22 g (0.01mole) of ethyl-α-cyclohexylphenylacetate were dissolve in 50 ml of drytoluene and 0.1 g of sodium hydride was added thereto as a catalyst. Themixture was charged into a Teflon Spinning Band rectification tower andethanol formed as a by-product was removed while heating and stirring.The reaction was completed in about 1 hour, and the reaction mixture wasallowed to stand and cooled to room temperature and poured into 30 g ofice-water. The layers were separated to remove the toluene layer and thetoluene layer was washed with saturated aqueous sodium chloride. Toluenewas removed under reduced pressure, and the resulting crude ester wassubjected to a column packed with 50 g of activated alumina usingbenzene-n-hexane (1:3) as an eluent to obtain 2.79 g (72% theoreticalyield) of the purified ester as white crystals. Melting point, 51°-53°C.

ν_(max) ^(nujol) 3035, 1738, 1606, 1500, 1454, 1155 cm.sup.⁻¹

δ_(ppm) ^(CCl) 7.3 - 6.9 (m. 11H), 5.80 (bs. 1H), 4.77 (AB. q 2H), 3.70(S. 2H), 3.06 (d. 2H, J=10Hz), 2.1 - 0.6 (m. 10H)

PREPARATION 5 Preparation ofdimethylmaleimidomethyl-α-allylphenylacetate (Compound No. 5)

1.74 g (0.01 mole) of N-chloromethyldimethylmaleimide and 2.93 g (0.01mole) of silver α-allylphenylacetate were added to 25 ml ofdimethylformamide and the mixture was allowed to stand overnight at roomtemperature. The precipitated crystals were filtered anddimethylformamide was distilled off under reduced pressure. Theresulting crude ester was subjected to a silica gel column (90 g) usinga mixture of chloroform-carbon tetrachloride (2:1) as an eluent toobtain 2.43 g (75% theoretical yield) of the desired ester as a whiteoily substance.

n_(D) ²².0 1.5349

ν_(max).^(film) 1780, 1740, 1720, 1640, 1600, 1140, 910 cm.sup.⁻¹

δ_(ppm) ^(CDCl).spsb.3 7.15 (S. 5H), 6.0 - 4.9 (m. 3H), 3.48 (t. 3H,J=10Hz), 3.0 - 2.0 (m. 2H), 2.0 (S. 6H)

PREPARATION 22 Preparation of5'-benzyl-3'-furylmethyl-α-isopropyl-4-methoxyphenylacetate (CompoundNo. 22)

1.90 g (0.01 mole) of 5'-benzyl-3-furfuryl alcohol and 1.58 g (0.02mole) of pyridine were dissolved in 50 ml of dry benzene, and 2.30 g(0.01 mole) of α-isopropyl-4-methoxyphenylacetyl chloride dissolved in 5ml of dry benzene was added dropwise to the solution over about 30minutes. After completion of the addition, the mixture was stirred atroom temperature for 3 hours to complete the reaction. The reactionmixture was poured into 50 g of ice-water followed by separating thebenzene layer, and the aqueous layer was extracted with two 20 mlportions of benzene. The combined benzene layer was washed successivelywith 5% hydrochloric acid, saturated aqueous sodium bicarbonate andsaturated aqueous sodium chloride. A yellow oily substance obtainedafter removal of benzene was subjected to a column packed with 25 g ofactivated alumina using benzene-n-hexane (1:3) as an eluent to obtain3.33 g (83.0% theoretical yield) of the purified ester as a colorlessoily substance.

n_(D) ¹⁷ 1.5470

ν_(max).^(film) 1735, 1617, 1515, 1250, 1032, 830, 730 cm.sup.⁻¹

δ_(ppm) ^(CCl).spsb.4 0.65 (d, 3H, J=7Hz), 0.95 (d. 3H, J=7Hz), 1.7- 2.5(m. 1H), 2.97 (d. 1H, J=11Hz), 3.67 (S. 3H), 3.81 (S. 2H), 4.78 (d.d.2H), 5.83 (b.S. 1H), 6.90 (d.d. 4H), 7.1- 7.3 (m. 6H)

PREPARATION 27 Preparation of3,4,5,6-tetrahydrophthalimidomethyl-α-ethyl-2,4,6-trimethylphenylacetate(Compound No. 27)

10.31 g (0.05 mole) of α-ethyl-2,4,6-trimethylphenylacetic acid and 9.05g (0.05 mole) of 3,4,5,6-tetrahydrophthalimidomethylol were dissolved in100 ml of dry benzene, and 16.51 g (0.08 mole) ofdicyclohexylcarbodiimide was added to the solution. The mixture was thenallowed to stand overnight in a sealed vessel. On next day, the mixturewas heated at reflux to complete the reaction, and, after allowing tocool, the precipitated dicyclohexylurea was separated by filtration. Aviscous oily substance obtained by concentration of the filtrate wassubjected to a silica gel column (360 g) to obtain 11.3 g (61.18%theoretical yield) of the purified ester as a colorless viscous oilysubstance.

n_(D) ²⁵ 1.5399

ν_(max).^(film) 1780, 1740, 1720, 1511, 1405, 1140 cm⁻ ¹

δ_(ppm) ^(CCl).spsb.4 0.85 (t. 3H, J=7Hz), 1.5-2.3 (m. 2H), 2.3 (b.S.9H), 3.32 (t. 3H, J=8Hz), 1.5-2.0 (m. 4H), 2.0-2.5 (m. 4H), 5.34 (d.d.2H), 7.0-7.3 (m. 2H)

PREPARATION 47 Preparation of2'-allyl-3'-methyl-2'-cyclopentene-1'-one-4'-yl-α-ethyl-3-methoxyphenylacetate (Compound No. 93)

7.41 g (0.02 mole) of α-ethyl-3-methoxyphenylacetic anhydride and 1.52 g(0.01 mole) of 2-allyl-3-methyl-4-hydroxy-2-cyclopentene-1-one weredissolved in 50 ml of dry pyridine, and the mixture was stirredovernight at room temperature. On next day, the reaction mixture waspoured into 100 g of ice-water and extracted with three 20 ml portionsof ethyl ether. The combined ether layer was then extracted with two 30ml portions of 5% aqueous sodium hydroxide to remove a carboxylic acidformed as a by-product. The ether layer was washed successively with 10%aqueous hydrochloric acid, saturated aqueous sodium bicarbonate andsaturated aqueous sodium chloride and dried over anhydrous sodiumsulfate. Removal of ether under reduced pressure yielded 3.2 g of acrude ester. The product was then subjected to a column packed with 20 gof activated alumina using benzene-n-hexane (1:3) as an eluent to obtain2.73 g (83.1% theoretical yield) of the desired ester.

n_(D) ¹⁹ 1.5211

ν_(max).^(film) 1730, 1710, 1150, 1140, 1000, 910 cm⁻ ¹

δ_(ppm) ^(CCl).spsb.4 0.90 (t. 3H, J=8Hz), 1.5-3.0 (m. 11H), 3.36 (t.1H, J=9Hz), 3.67 (S. 1H), 4.7-6.0 (m. 3H), 6.5-6.9 (m. 4H)

PREPARATION 46 Preparation of3'-phenoxybenzyl-α-isopropyl-3-methoxyphenylacetate (Compound No. 87)

8.01 g (0.04 mole) of m-phenoxybenzyl alcohol and 7.09 g (0.03 mole) ofethyl α-isopropyl-3-methoxyphenylacetate were dissolved in 100 ml of drytoluene, and 0.1 g of sodium hydride was added thereto as a catalyst.The mixture was then charged in a Teflon Spinning Band rectifier towerhaving a length of 50 cm and heated while stirring. The reaction wascompleted in about 3 hours by removing ethanol as an azeotropicdistillation with toluene at the top of the tower. After allowing tostand and cooling the mixture was poured into cold water to separatelayers. Removal of toluene by distillation under reduced pressureyielded 11.5 g of a crude ester. The product was then subjected to acolumn packed with 55 g of activated alumina using benzene-n-hexane(1:3) as an eluent to obtain 10.12 g (86.4% theoretical yield based onthe starting ethyl ester of the desired ester.

n_(D) ¹⁷ 1.5377

ν_(max).^(film) 3060, 1738, 1590, 1490, 1255, 1145, 775, 690 cm⁻ ¹

δ_(ppm) ^(CCl).spsb.4 0.70 (d. 3H, J=7Hz), 0.97 (d. 3H, J=7Hz), 0.9-2.6(m. 1H), 3.08 (d. 1H, J=11Hz), 3.65 (S. 3H), 4.95 (AB Type d.d. 2H),6.5-7.4 (m. 13H)

PREPARATION 48 Preparation of3'-phenoxybenzyl-2-(1',2',3',4'-tetrahydronaphthalene-8'-yl) isovalerate(Compound No. 43)

3.95 g (0.015 mole) of m-phenoxybenzyl bromide, 2.32 g (0.01 mole) of2-(1',2',3',4'-tetrahydronaphthalene-8'-yl) isovaleric acid and 2.02 g(0.02 mole) of triethylamine were added to 50 ml of dimethylformamideand the mixture was stirred overnight at room temperature. The reactionmixture was poured into 50 g of ice-water and extracted with three 30 mlportions of ethyl ether. The combined ether layer was washedsuccessively with 5% hydrochloric acid, saturated aqueous sodiumbicarbonate and saturated aqueous sodium chloride and dried overanhydrous sodium sulfate. Removal of ethyl ether by distillation underreduced pressure yielded a crude ester which was then subjected to acolumn packed with 20 g of activated alumina using benzene-n-hexane(1:3) as an eluent to obtain 3.45 g (83.2% theoretical yield based onthe carboxylic acid stating material) of the desired ester as acolorless oily substance.

n_(D) ¹⁹ 1.5660

ν_(max).^(film) 3060, 1736, 1588, 1490, 1255, 770, 690 cm⁻ ¹

δ_(ppm) ^(CCl).spsb.4 0.68 (d. 3H, J=7Hz), 1.03 (d. 3H, J=7Hz), 1.5-2.0(m. 4H), 2.1-2.6 (m. 1H), 2.5-3.0 (m. 4H), 2.48 (d. 1H, J=11Hz), 4.74(S. H), 6.6-7.4 (m. 12H)

In a similar manner as described in Preparations 1, 2, 5, 17, 22, 27, 46and 48, the compounds listed in Table below were obtained. In the table,the symbols "a", "b", "c", "d" and "e" stand for the followingesterification methods.

a. Esterification using an acid chloride.

b. Esterification using an acid anhydride.

c. Dehydration esterification of an acid and an alcohol withdicyclohexylcarbodiimide in an inert solvent.

d. Esterification by transesterification using sodium hydride as acatalyst in toluene.

e. Esterification using a silver or a triethylammonium salt of acid anda halide of an alcohol.

Representative compounds of this invention prepared by the above methodsare shown below, but they are not to be construed as limiting thepresent invention.

      Prepa-   Esteri-  Physical  ration Comp.  fication Yield Properties     Exp.No. No.   Z   Y      OX Method (%) Calcd. (%) Found (%)                            1 1     CH.sub.3      CH.sub.2     ##STR150##      ##STR151##      b 85 C.sub.22 H.sub.22 O.sub.3C: 79.01H:      6.63 n.sub.D.sup.17 1.554578.91 6.54  2 2 CH.sub.3      CH.sub.2     ##STR152##      ##STR153##      a 91 C.sub.23 H.sub.22 O.sub.3C: 79.74H:      6.40 n.sub.D.sup.22 1.571279.65 6.41  3 3 CH.sub.3 CH.sub.2      O     ##STR154##      ##STR155##      e 80 C.sub.23 H.sub.22 O.sub.4C: 76.22H:      6.12 n.sub.D.sup.24 1.527576.19 6.17  4 4 CH.sub.3      CH.sub.2     ##STR156##      ##STR157##      a 92 C.sub.19 H.sub.17 O.sub.4 NC: 70.57H:  5.30N:  4.33 n.sub.D.sup.22     1.540370.61 5.28 4.25      5 5 CH.sub.2CHCH.sub.2     ##STR158##      ##STR159##      e 75 C.sub.18 H.sub.19 O.sub.4 NC: 68.99H:  6.11N:  4.47 n.sub.D.sup.22     1.534967.01 6.09 4.42  6 6 CH.sub.3      CH.sub.2     ##STR160##      ##STR161##      a 81 C.sub.16 H.sub.16 O.sub.3 SC: 66.64H:  5.59S: 11.12 n.sub.D.sup.22     1.583566.59 5.5011.18      7 7 CH.sub.3     ##STR162##      ##STR163##      e 85 C.sub.18 H.sub.23 O.sub.4 NC: 68.12H:  7.31N:  4.41 n.sub.D.sup.23     1.564868.09 7.22 4.50  8 8 CH.sub.3      CH.sub.2     ##STR164##      ##STR165##      a 83 C.sub.20 H.sub.18 O.sub.3C: 78.41H:  5.92 n.sub.D.sup.24.5     1.531078.3 5.86  9 9 CH.sub.3      CH.sub.2     ##STR166##      ##STR167##      a 84 C.sub.22 H.sub.24 O.sub.4C: 74.97H:      6.86 n.sub.D.sup.22 1.512375.06 6.80  10 10 CH.sub.3      CH.sub.2     ##STR168##      ##STR169##      a 90 C.sub.20 H.sub.20 O.sub.2C: 82.15H:      6.89 n.sub.D.sup.23 1.503982.05 6.93      11 11 CH.sub.3     ##STR170##      ##STR171##      a 93 C.sub.20 H.sub.22 O.sub.2C: 81.60H:      7.53 n.sub.D.sup.24 1.553681.52 7.58  12 12 CH.sub.3      CH.sub.2     ##STR172##      ##STR173##      a 91 C.sub.22 H.sub.22 O.sub.2 SC: 75.39H:  6.32S:  9.15 n.sub.D.sup.22     1.548875.29 6.27 9.20      13 13     ##STR174##      ##STR175##      ##STR176##      a 90 C.sub.23 H.sub.24 O.sub.2 SC: 75.78H:  6.64S:  8.79 n.sub.D.sup.22     1.561375.70 6.69 8.81  14 14 CH.sub.3      CH.sub.2     ##STR177##      ##STR178##      a 71 C.sub.24 H.sub.21 O.sub.3 NC: 77.60H:  5.70N:  3.77 n.sub.D.sup.21     1.563877.49 5.97 3.79  15 15 BrCH.sub.2      CH.sub.2     ##STR179##      ##STR180##      a 89 C.sub.22 H.sub.21 O.sub.3 BrC: 64.08H:      5.13Br:19.38 n.sub.D.sup.23 1.591164.11 5.1119.29  16 16 CH.sub.3     CH.sub.2      ##STR181##      ##STR182##      a 90 C.sub.17 H.sub.20 O.sub.3C: 70.81H:      6.99 n.sub.D.sup.22 1.511870.89 6.77      17 17     ##STR183##      ##STR184##      ##STR185##      d 72 C.sub.26 H.sub.28 O.sub.3C: 80.38H:  7.27 mp 51-53° C80.41     7.24  18 18 CH.sub.3      CH.sub.2     ##STR186##      ##STR187##      a 84 C.sub.21 H.sub.26 O.sub.3C: 77.27H:      8.03 n.sub.D.sup.23 1.541777.41 7.96      19 19     ##STR188##      ##STR189##      ##STR190##      a 80 C.sub.21 H.sub.22 O.sub.3C: 78.23H:      6.88 n.sub.D.sup.24 1.563278.19 6.94      20 20 CH.sub.2CHCH.sub.2     ##STR191##      ##STR192##      a 90 C.sub.17 H.sub.16 O.sub.3 SC: 67.98H:  5.37S: 10.68 n.sub.D.sup.22     1.527468.07 5.3610.64      21 21 CH.sub.3     ##STR193##      ##STR194##      a 88 C.sub.20 H.sub.24 O.sub.3C: 76.89H:      7.74 n.sub.D.sup.21 1.569376.80 7.71      22 22     ##STR195##      ##STR196##      ##STR197##      a 88 C.sub.24 H.sub.26 O.sub.4C: 76.16H:      6.93 n.sub.D.sup.17 1.547076.20 6.89  23 23 CH.sub.3      CH.sub.2     ##STR198##      ##STR199##      b 83.2 C.sub.23 H.sub.24 O.sub.4C: 75.80H:  6.64 n.sub.D.sup.25     1.548175.71 6.69      24 24     ##STR200##      ##STR201##      ##STR202##      e 79.8 C.sub.26 H.sub.28 O.sub.5C: 74.26H:  6.71 n.sub.D.sup.25     1.565574.25 6.77  25 25 CH.sub.3      CH.sub.2     ##STR203##      ##STR204##      e 81.5 C.sub.25 H.sub.24 O.sub.5C: 74.24H:  5.98 n.sub.D.sup.25     1.562174.11 6.09  26 26 CH.sub.3      CH.sub.2     ##STR205##      ##STR206##      a 90.1 C.sub.23 H.sub.24 O.sub.4 SC: 69.67H:  6.10S:      8.09 n.sub.D.sup.25 1.544869.55 6.11 8.11  27 27 CH.sub.3 CH.sub.2      ##STR207##      ##STR208##      c 61.2 C.sub.22 H.sub.27 O.sub.4 NC: 71.52H:  7.37N:      3.79 n.sub.D.sup.25 1.539971.60 7.29 3.85      28 28     ##STR209##      ##STR210##      ##STR211##      a 92.2 C H.sub.21 O.sub.3 F.sub.3C: 66.66H:      5.59F: 15.06 n.sub.D.sup.25 1.536866.61 5.6215.11      29 30 CH.sub.2CHCH.sub.2      ##STR212##      ##STR213##      a 82.5 C.sub.22 H.sub.24 O.sub.4C: 74.97H:  6.86 n.sub.D.sup.25     1.556675.02 6.04      30 33     ##STR214##      ##STR215##      ##STR216##      e 81.8 C.sub.24 H.sub.24 O.sub.6C: 70.57H:  5.92 n.sub.D.sup.25     1.536770.56 5.89      31 34     ##STR217##      ##STR218##      ##STR219##      a 92.5 C.sub.27 H.sub.27 O.sub.4 NC: 75.50H:  6.34N:      3.26 n.sub.D.sup.25 1.520875.19 6.30 3.31      32 35     ##STR220##      ##STR221##      ##STR222##      a 95.3 C.sub.24 H.sub.26 O.sub.3 SC: 73.06H:  6.64S:      8.13 n.sub.D.sup.25 1.533573.10 6.64 8.15      33 37     ##STR223##      ##STR224##      ##STR225##      a 73.6 C.sub.22 H.sub.20 O.sub.5C: 72.51H:  5.53 n.sub.D.sup.25     1.523672.55 5.61      34 36     ##STR226##      ##STR227##      ##STR228##      d 86.2 C.sub.27 H.sub.30 O.sub.3C: 80.56H:  7.51 80.61 7.46  35 45     CH.sub.3      CH.sub.2     ##STR229##      ##STR230##      e 78.1 C.sub.26 H.sub.24 O.sub.3C: 81.22H:  6.29 81.20 6.31  36 48      ##STR231##      ##STR232##      ##STR233##      a 92.7 C.sub.23 H.sub.25 O.sub.5 NC: 69.85H:  6.37N:      3.54 n.sub.D.sup.25 1.522169.78 6.39 3.55      37 49     ##STR234##      ##STR235##      ##STR236##      a 91.2 C.sub.25 H.sub.29 O.sub.2 ClC: 75.64H:  7.36Cl:      8.93 n.sub.D.sup.25 1.541375.66 7.39 8.87      38 51     ##STR237##      ##STR238##      ##STR239##      a 84.6 C.sub.22 H.sub.22 O.sub.4C: 75.41H:  6.33 n.sub.D.sup.26     1.525375.40 6.22  39 52 CH.sub.3      CH.sub.2     ##STR240##      ##STR241##      a 81.2 C.sub.22 H.sub.24 O.sub.3 SC: 71.71H:  6.56S:      8.70 n.sub.D.sup.25 1.554971.80 6.59 8.78  40 55 CH.sub.2CHCH.sub.2      ##STR242##      ##STR243##      a 86.9 C.sub.22 H.sub.21 O.sub.5 NSC: 64.21H:  5.15N  3.40S:  7.79     n.sub.D.sup.19 1.535064.30 5.19 3.29 7.72      41 56     ##STR244##      ##STR245##      ##STR246##      c 72.1 C.sub.23 H.sub.26 O.sub.5 SC: 66.64H:  6.32 S:      7.14 n.sub.D.sup.22 1.532466.57 6.40 7.71      42 67     ##STR247##      ##STR248##      ##STR249##      a 93.7 C.sub.21 H.sub.24 O.sub.4C: 74.09H:  7.11 n.sub.D.sup.25     1.562874.06 7.22      43 61     ##STR250##      ##STR251##      ##STR252##      a 93.2 C.sub.24 H.sub.26 O.sub.5C: 73.07H:  6.64 n.sub.D.sup.25     1.550173.11 6.57 44 69 CH.sub.3      CH.sub.2     ##STR253##      ##STR254##      b 78.9 C.sub.21 H.sub.19 O.sub.3 F.sub.3C: 67.01H:  5.09F: 15.15     n.sub.D.sup.25 1.511966.95 5.1415.20      45 81     ##STR255##      ##STR256##      ##STR257##      d 84.8 C.sub.24 H.sub.26 O.sub.4C: 76.16H:  6.93 n.sub.D.sup.16     1.541176.22 6.94      46 87     ##STR258##      ##STR259##      ##STR260##      d 86.4 C.sub.25 H.sub.26 O.sub.4C: 76.90H:  6.71 n.sub.D.sup.17     1.537776.85 6.76  47 93 CH.sub.3      CH.sub.2     ##STR261##      ##STR262##      b 83.1 C.sub.20 H.sub.24 O.sub.4C: 73.14H:  7.37 n.sub.D.sup.19     1.521173.19 7.30      48 43     ##STR263##      ##STR264##      ##STR265##      e 83.2 C.sub.28 H.sub.30 O.sub.3C: 81.12H:  7.30 n.sub.D.sup.20     1.566081.20 7.27  49 102 CH.sub.3      CH.sub.2     ##STR266##      ##STR267##      a 91 C.sub.23 H.sub.24 O.sub.3C: 79.28H:      6.94 n.sub.D.sup.25 1.547479.32 7.10      50 103     ##STR268##      ##STR269##      ##STR270##      a 90 C.sub.24 H.sub.26 O.sub.3C: 79.53H:      7.23 n.sub.D.sup.25 1.543379.60 7.18  51 104 CH.sub.3      CH.sub.2     ##STR271##      ##STR272##      a 89 C.sub.23 H.sub.24 O.sub.3C: 79.28H:      6.94 n.sub.D.sup.25 1.547079.23 6.99      52 105     ##STR273##      ##STR274##      ##STR275##      a 93 C.sub.24 H.sub.26 O.sub.3C: 79.53H:  7.23 n.sub.D.sup.25.5     1.543079.50 7.30      53 106     ##STR276##      ##STR277##      ##STR278##      a 92 C.sub.25 H.sub.28 O.sub.3C: 79.75H:  7.50 n.sub.D.sup.25.5     1.523879.79 7.49      54 107     ##STR279##      ##STR280##      ##STR281##      a 91 C.sub.23 H.sub.23 O.sub.3 ClC: 72.15H:  6.05Cl:      9.26 n.sub.D.sup.25.5 1.524172.18 6.10 9.29      55 108     ##STR282##      ##STR283##      ##STR284##      a 90 C.sub.25 H.sub.26 O.sub.3C: 80.18H:  7.00 n.sub.D.sup.28.5     1.559680.21 6.92      56 109     ##STR285##      ##STR286##      ##STR287##      a 94 C.sub.24 H.sub.26 O.sub.3C: 77.53H:  7.23 n.sub.D.sup.26.5     1.543179.60 7.21  57 110 CH.sub.3      CH.sub.2     ##STR288##      ##STR289##      a 89 C.sub.23 H.sub.24 O.sub.3C: 79.28H:  6.94 n.sub.D.sup.26.5     1.550179.40 7.11      58 129     ##STR290##      ##STR291##      ##STR292##      b 85 C.sub.23 H.sub.25 O.sub.2 ClC: 74.88H:  6.83Cl:      9.61 n.sub.D.sup.20 1.542374.79 6.81 9.63      59 130     ##STR293##      ##STR294##      ##STR295##      e 68 C.sub.20 H.sub.18 O.sub.4 NClC: 64.60H:  4.88N:  3.77Cl:  9.54     n.sub.D.sup.20 1.550164.63 4.86 3.79 9.53      60 131     ##STR296##      ##STR297##      ##STR298##      e 69 C.sub.20 H.sub.18 O.sub.4 NBrC: 57.70H:  4.36N:  3.37Br:19.20     n.sub.D.sup.20 1.538357.80 4.39 3.3719.28      61 132     ##STR299##      ##STR300##      ##STR301##      a 88 C.sub.26 H.sub.32 O.sub.2C: 82.93H:      8.57 n.sub.D.sup.20 1.543382.88 8.63      62 133     ##STR302##      ##STR303##      ##STR304##      a 92 C.sub.22 H.sub.23 O.sub.2 Cl.sub.5C: 53.20H:  4.67 Cl:35.69     n.sub.D.sup.20 1.521153.38 4.6835.71      63 134     ##STR305##      ##STR306##      ##STR307##      a 93 C.sub.23 H.sub.28 O.sub.2C: 82.10H:  8.39 82.19  8.41  64 135      ##STR308##      ##STR309##      ##STR310##      a 89 C.sub.21 H.sub.23 O.sub.2 FC: 77.27H:  7.10F:  5.82 77.32 7.03     5.91      65 136     ##STR311##      ##STR312##      ##STR313##      a 89 C.sub.21 H.sub.21 O.sub.3 NSC: 68.64H:  5.76N:  3.81S:  8.73     n.sub.D.sup.20 1.533568.67 5.81 3.80 8.79      66 137     ##STR314##      ##STR315##      ##STR316##      d 81 C.sub.23 H.sub.28 O.sub.2C: 82.10 H:      8.39 n.sub.D.sup.20 1.529982.15 8.30      67 138     ##STR317##      ##STR318##      ##STR319##      d 87 C.sub.22 H.sub.25 O.sub.2 ClC: 74.04H:  7.06Cl:      9.94 n.sub.D.sup.20 1.541474.08 7.1010.03      68 139     ##STR320##      ##STR321##      ##STR322##      b 79 C.sub.19 H.sub.17 O.sub.2 Cl.sub.5C: 50.19H:  3.77Cl:39.01     n.sub.D.sup.20 1.538250.22 3.7939.13      69 140     ##STR323##      ##STR324##      ##STR325##      a 69 C.sub.20 H.sub.17 O.sub.2 FCl.sub.2C: 63.34H:  4.52F:      5.01Cl:18.70 n.sub.D.sup.20 1.528863.39 4.46 5.0818.80      70 141     ##STR326##      ##STR327##      ##STR328##      a 78 C.sub.22 H.sub.20 O.sub.2 F.sub.3C: 70.76H:      5.40F: 15.27 n.sub.D.sup.20 1.538570.80 5.3915.27      71 142     ##STR329##      ##STR330##      ##STR331##      a 82 C.sub.22 H.sub.26 O.sub.2C: 81.95H:      8.13 n.sub.D.sup.20 1.523682.06 8.12      72 143     ##STR332##      ##STR333##      ##STR334##      a 80 C.sub.24 H.sub.30 O.sub.2C: 82.24H:      8.63 n.sub.D.sup.20 1.534182.19 8.66      73 144     ##STR335##      ##STR336##      ##STR337##      a 83 C.sub.21 H.sub.23 O.sub.2 ClC: 73.56H:      6.76Cl:10.34 n.sub.D.sup.20 1.549173.51 6.8110.29      74 145     ##STR338##      ##STR339##      ##STR340##      b 86 C.sub.22 H.sub.24 O.sub.3 SC: 71.71 H:  6.56S:      8.70 n.sub.D.sup.20 1.537271.73 6.60 8.79      75 146     ##STR341##      ##STR342##      ##STR343##      a 92 C.sub.21 H.sub.24 O.sub.3C: 77.75H:      7.46 n.sub.D.sup.20 1.537777.77 7.40      76 147     ##STR344##      ##STR345##      ##STR346##      a 95 C.sub.18 H.sub.20 O.sub.4 NClC: 61.80H:  5.76N:  4.01Cl:10.14     n.sub.D.sup.20 1.546961.90 5.73 4.0210.19      77 148     ##STR347##      ##STR348##      ##STR349##      b 87 C.sub.22 H.sub.25 O.sub.2 ClC: 74.04H:  7.06Cl:      9.94 n.sub.D.sup.20 1.547174.11 7.92 9.90      78 149     ##STR350##      ##STR351##      ##STR352##      a 84 C.sub.23 H.sub.26 O.sub.2 ClC: 74.68H:  7.09Cl:      9.59 n.sub.D.sup.20 1.548374.77 7.12 9.52      79 150     ##STR353##      ##STR354##      ##STR355##      a 89 C.sub.21 H.sub.26 O.sub.2 SC: 73.64H:  7.65S:       9.36 n.sub.D.sup.20 1.539673.66 7.64 9.50      80 151     ##STR356##      ##STR357##      ##STR358##      a 95 C.sub.21 H.sub.21 O.sub.2 ClC: 74.00H:      6.21Cl:10.40 n.sub.D.sup.20 1.561174.11 6.2310.36      81 152     ##STR359##      ##STR360##      ##STR361##      e 82 C.sub.20 H.sub.22 O.sub.4 NFC: 66.84H:  6.17N:  3.90F:  5.29     n.sub.D.sup.20 1.522966.88 6.18 4.01 5.30      82 153     ##STR362##      ##STR363##      ##STR364##      b 80 C.sub.21 H.sub.26 O.sub.3C: 77.27H:      8.03 n.sub.D.sup.20 1.538777.20 8.09      83 154     ##STR365##      ##STR366##      ##STR367##      a 89 C.sub.20 H.sub.21 O.sub.3 FC: 73.15H:  6.45F:  5.79 n.sub.D.sup.20     1.531673.19 6.50 5.81      84 155     ##STR368##      ##STR369##      ##STR370##      a 93 C.sub.24 H.sub.26 O.sub.3C: 79.53H:      7.23 n.sub.D.sup.20 1.545279.55 7.33      85 156     ##STR371##      ##STR372##      ##STR373##      a 92 C.sub.23 H.sub.23 O.sub.3 ClC: 72.15H:  6.05Cl:      9.26 n.sub.D.sup.20 1.544872.18 6.00 9.32      86 157     ##STR374##      ##STR375##      ##STR376##      a 92 C.sub.23 H.sub.23 O.sub.3 IC: 58.24H:  4.89I: 26.76 n.sub.D.sup.20     1.535258.22 4.9326.88      87 158     ##STR377##      ##STR378##      ##STR379##       a 96 C.sub.24 H.sub.26 O.sub.2 SC: 76.15H:  6.92S:      8.47 n.sub.D.sup.19 1.531176.16 7.03 8.46      88 159     ##STR380##      ##STR381##      ##STR382##      a 86 C.sub.26 H.sub.30 O.sub.2 SC: 76.80H:  7.44S:  7.89 n.sub.D.sup.19     1.534276.77 7.51 7.82      89 160     ##STR383##      ##STR384##      ##STR385##      a 81 C.sub.22 H.sub.22 O.sub.3C: 79.01H:      6.63 n.sub.D.sup. 26 1.526279.22 6.58      90 161     ##STR386##      ##STR387##      ##STR388##      a 76 C.sub.23 H.sub.24 O.sub.3C: 79.28H:      6.94 n.sub.D.sup.22 1.529179.33 7.10      91 162     ##STR389##      ##STR390##      ##STR391##      a 92 C.sub.22 H.sub.26 O.sub.2C: 81.95H:      8.13 n.sub.D.sup.20 1.536682.00 8.18      92 163     ##STR392##      ##STR393##      ##STR394##      a 87 C.sub.26 H.sub.30 O.sub.3 SC: 73.90H:  7.16S:  7.59 n.sub.D.sup.20     1.536173.92 7.17 7.63      93 164     ##STR395##      ##STR396##      ##STR397##      a 88 C.sub.22 H.sub.21 O.sub.3 SFC: 68.73H:  5.51S:  8.34F:  4.94     n.sub.D.sup.20 1.483768.77 5.48 8.36 4.90      94 165     ##STR398##      ##STR399##      ##STR400##      a 88 C.sub.25 H.sub.22 O.sub.3 NFC: 74.42H:  5.50N:  3.47F:  4.71     n.sub.D.sup. 20 1.523374.49 5.56 3.49 4.79      95 166     ##STR401##      ##STR402##      ##STR403##      a 92 C.sub.22 H.sub.21 O.sub.3 SBrC: 59.33H:  4.75S:  7.20Br:17.94     n.sub.D.sup.20 1.581159.36 4.79 7.1117.92      96 167     ##STR404##      ##STR405##      ##STR406##      d 91 C.sub.25 H.sub.23 O.sub.2 BrC: 68.97H:      5.32Br:18.36 n.sub.D.sup.20 1.580268.96 5.3318.40      97  168     ##STR407##      ##STR408##      ##STR409##      a 93 C.sub.27 H.sub.32 O.sub.3C: 80.16H:      7.97 n.sub.D.sup.20 1.538780.15 7.96  98 169 C.sub.2      H.sub.5     ##STR410##      ##STR411##      a 79 C.sub.18 H.sub.17 O.sub.3 FC: 71.98H:  5.71F:  6.33 n.sub.D.sup.20     1.521871.99 5.76 6.27  99 170 C.sub.2      H.sub.5     ##STR412##      ##STR413##      b 82 C.sub.21 H.sub.20 O.sub.3C: 78.72H:      6.29 n.sub.D.sup.26 1.526178.77 6.22  100 171 C.sub.2      H.sub.5     ##STR414##      ##STR415##      e 89 C.sub.26 H.sub.28 O.sub.3C: 80.38H:      7.27 n.sub.D.sup.19 1.553680.29 7.33  101 172 C.sub.2      H.sub.5     ##STR416##      ##STR417##      e 82 C.sub.22 H.sub.22 O.sub.3 SC: 72.10H:  6.05S:  8.75 n.sub.D.sup.19     1.549972.16 6.07 8.82  102 173 C.sub.2      H.sub.5     ##STR418##      ##STR419##      a 93 C.sub.20 H.sub.21 O.sub.2 ClC: 73.05H:      6.44Cl:10.78 n.sub.D.sup.20 1.523673.09 6.4610.69  103 174 C.sub. 2     H.sub.5      ##STR420##      ##STR421##      a 92 C.sub.21 H.sub.22 O.sub.2C: 82.32H:      7.24 n.sub.D.sup.20 1.525282.40 7.26  104 175 C.sub.2      H.sub.5     ##STR422##      ##STR423##      a 86 C.sub.20 H.sub.19 O.sub.4 BrC: 59.56H:      4.75Br:19.82 n.sub.D.sup.20 1.523359.61 4.7720.91  105 176 C.sub.2     H.sub.5      ##STR424##      ##STR425##      e 92 C.sub.24 H.sub.24 O.sub.3C: 79.97H:      6.71 n.sub.D.sup.20 1.571180.05 6.77      106 177 C.sub.2 H.sub.5     ##STR426##      ##STR427##      e 96 C.sub.23 H.sub.21 O.sub.3 ClC: 72.53H:  5.56Cl:      9.31 n.sub.D.sup.21.5 1.573272.51 5.46 9.33  107 178 C.sub.2 H.sub.5      ##STR428##      ##STR429##      e 89 C.sub.23 H.sub.21 O.sub.3 BrC: 64.95H:      4.98Br:18.79 n.sub.D.sup.17 1.586164.92 4.8618.82  108 179 C.sub.2     H.sub.5      ##STR430##      ##STR431##      a 82 C.sub.23 H.sub.23 O.sub.3 IC: 58.24H:  4.89I: 26.76 n.sub.D.sup.20     1.573358.25 4.9228.81   109 180 C.sub.2      H.sub.5     ##STR432##      ##STR433##      b 76 C.sub.21 H.sub.19 O.sub.4 ClC: 68.01H:  5.16Cl:      9.56 n.sub.D.sup.20 1.562566.06 5.22 9.62      110 181 CH.sub.3     ##STR434##      ##STR435##      a 90 C.sub.22 H.sub.22 O.sub.3C: 79.01H:      6.63 n.sub.D.sup.25 1.547179.07 6.58      111 182 CH.sub.3     ##STR436##      ##STR437##      a 91 C.sub.21 H.sub.19 O.sub.3 ClC: 71.08H:  5.40Cl:      9.99 n.sub.D.sup.22 1.551871.11 5.32  9.89      112 183 CH.sub.3     ##STR438##      ##STR439##      e 87 C.sub.23 H.sub.22 O.sub.3C: 79.74H:      6.40 n.sub.D.sup.28 1.559279.77 6.36  113 184 C.sub.2      H.sub.5     ##STR440##      ##STR441##      a 88 C.sub.22 H.sub.21 O.sub.3 ClC: 71.63H:  5.74Cl:      9.61 n.sub.D.sup.25 1.554971.66 5.81 9.70  114 185 C.sub.2 H.sub.5      ##STR442##      ##STR443##      a 87 C.sub.22 H.sub.21 O.sub.3 FC: 74.98H:  6.00F:  5.39 n.sub.D.sup.20     1.443775.03 6.02  5.29  115 186 C.sub.2      H.sub.5     ##STR444##      ##STR445##      a 83 C.sub.22 H.sub.21 O.sub.2 SFC: 71.71H:  5.75S:  8.70F:  5.16     n.sub.D.sup.20 1.493371.77 5.76 8.81 5.13  116 187 C.sub.2 H.sub.5      ##STR446##      ##STR447##      e 76 C.sub.19 H.sub.20 O.sub.4 NClC: 63.07 H:  5.57N:  3.87Cl:  9.80     n.sub.D.sup.20 1.531662.98 5.54 3.92 9.69  117 188 C.sub.2 H.sub.5      ##STR448##      ##STR449##      a 83  C.sub.20 H.sub.24 O.sub.3C: 76.89H:      7.74 n.sub.D.sup.20 1.522476.79 7.81  118 189 C.sub.2      H.sub.5     ##STR450##      ##STR451##      a 80 C.sub.20 H.sub.22 O.sub.3C: 77.39H:      7.14 n.sub.D.sup.20 1.545677.44 7.14  119 190 C.sub.2      H.sub.5     ##STR452##      ##STR453##      a 82 C.sub.19 H.sub.19 O.sub.3 ClC: 68.98H:      5.79Cl:10.72 n.sub.D.sup.20 1.544568.92 5.7810.85  120 191 C.sub.2     H.sub.5      ##STR454##      ##STR455##      a 90 C.sub.22 H.sub.21 O.sub.3 FC: 74.98H:  6.01F:  5.39 n.sub.D.sup.20     1.526774.87 6.02 5.41  121 192 C.sub.2      H.sub.5     ##STR456##      ##STR457##      a 92 C.sub.22 H.sub.21 O.sub.3 ClC: 71.63H:  5.74Cl:      9.61 n.sub.D.sup.20 1.535271.66 5.78 9.62      122 193     ##STR458##      ##STR459##      ##STR460##      a 90 C.sub.22 H.sub.24 O.sub.4C: 74.97H:      6.86 n.sub.D.sup.19 1.537775.10 6.86      123 194     ##STR461##      ##STR462##      ##STR463##      a 91 C.sub.21 H.sub.21 O.sub.4 ClC: 67.65H:  5.68Cl:      9.51 n.sub.D.sup.19 1.542167.62 5.72 9.61      124 195     ##STR464##      ##STR465##      ##STR466##      a 89 C.sub.23 H.sub.24 O.sub.4C: 75.80H:      6.64 n.sub.D.sup.20 1.523575.83 6.70      125 196     ##STR467##      ##STR468##      ##STR469##      a 91 C.sub.23 H.sub.23 O.sub.2 SCl C: 69.24H:  5.81S:  8.04Cl:  8.89     n.sub.D.sup.20 1.555169.26 5.84 8.11 8.92      126 197     ##STR470##      ##STR471##      ##STR472##      a 88 C.sub.24 H.sub.25 O.sub.3 BrC: 65.31H:      5.71Br:18.11 n.sub.D.sup.20 1.534965.33 5.8318.20      127 198     ##STR473##      ##STR474##      ##STR475##      a 92 C.sub.20 H.sub.23 O.sub.3 FC: 72.70H:  7.02F:  5.75 n.sub.D.sup.20     1.546672.69 7.11 5.72      128 199     ##STR476##      ##STR477##      ##STR478##      a 80 C.sub.19 H.sub.19 O.sub.3 ClC: 68.98H:      5.79Cl: 10.72 n.sub.D.sup.19 1.523869.01 5.7210.77      129 200     ##STR479##      ##STR480##      ##STR481##      a 82 C.sub.22 H.sub.22 O.sub.3C: 79.01H:      6.63 n.sub.D.sup.20 1.526579.10 6.58      130 201     ##STR482##      ##STR483##      ##STR484##      a 79 C.sub.21 H.sub.19 O.sub.3 ClC: 71.08H:  5.40Cl:      9.99 n.sub.D.sup.20 1.523371.00 5.46 9.89      131 202     ##STR485##      ##STR486##      ##STR487##      a 75 C.sub.21 H.sub.19 O.sub.3 FC: 74.54H:  5.66F:  5.62 n.sub.D.sup.20     1.524974.53 5.77 5.66      132 203     ##STR488##      ##STR489##      ##STR490##      a 83 C.sub.21 H.sub.19 O.sub.3 BrC: 63.17H:      4.80Br:20.02 n.sub.D.sup.20 1.528963.18 4.7920.04      133 204     ##STR491##      ##STR492##      ##STR493##      a 90 C.sub.23 H.sub.23 O.sub.3 ClC: 72.15H:  6.05Cl:      9.26 n.sub.D.sup.21 1.552172.16 6.11 9.39      134 205     ##STR494##      ##STR495##      ##STR496##      a 89 C.sub.23 H.sub.23 O.sub.3 ClC: 72.15H:  6.05Cl:      9.26 n.sub.D.sup.21 1.557672.14 6.09 9.31      135 206     ##STR497##      ##STR498##      ##STR499##      d 83 C.sub.24 H.sub.23 O.sub.3 ClC: 72.99H:  5.87Cl:      8.98 n.sub.D.sup.21 1.565573.04 5.87 8.99      136 207     ##STR500##      ##STR501##      ##STR502##      e 92 C.sub.24 H.sub.23 O.sub.3 ClC: 72.99H:  5.87Cl:      8.98 n.sub.D.sup.17 1.572272.93 5.89 9.00      137 208     ##STR503##      ##STR504##      ##STR505##      d 84 C.sub.23 H.sub.23 O.sub.3 FC: 75.39 H:  6.33F:      5.19 n.sub.D.sup.21 1.463775.42 6.31 5.22      138 209     ##STR506##      ##STR507##      ##STR508##      a 92 C.sub.23 H.sub.23 O.sub.3 FC: 75.39H:  6.33F:  5.19 n.sub.D.sup.21     1.533075.44 6.26 5.14      139 210     ##STR509##      ##STR510##      ##STR511##      d 93 C.sub.24 H.sub.23 O.sub.3 FC: 76.17H:  6.13F:  5.02 n.sub.D.sup.23     1.554476.20 6.14 5.10      140 211     ##STR512##      ##STR513##      ##STR514##      e 92 C.sub.24 H.sub.23 O.sub.3 FC: 76.17H:  6.13F:      5.02 n.sub.D.sup.21.5 1.554376.15 6.13  5.11      141 212     ##STR515##      ##STR516##      ##STR517##      a 89 C.sub.23 H.sub.23 O.sub.3 BrC: 64.64H:      5.42Br:18.70 n.sub.D.sup.17 1.565164.58 5.4418.96      142 213     ##STR518##      ##STR519##      ##STR520##      e 91 C.sub.24 H.sub.23 O.sub.3 BrC: 65.61H:      5.28Br:18.19 n.sub.D.sup.17.5 1.580265.62 5.3018.23      143 214     ##STR521##      ##STR522##      ##STR523##      a 82 C.sub.25 H.sub.28 O.sub.3C: 79.75H:  7.50 n.sub.D.sup.18.5     1.534779.81 7.51      144 215     ##STR524##      ##STR525##      ##STR526##      a 94 C.sub.26 H.sub.28 O.sub.3C: 80.38H:  7.27 n.sub.D.sup.21.5     1.559080.34 7.29      145 216     ##STR527##      ##STR528##      ##STR529##      a 92 C.sub.26 H.sub.30 O.sub.3C: 79.96H:  7.74 n.sub.D.sup.18      1.538780.01 7.70      146 217     ##STR530##      ##STR531##      ##STR532##      a 90 C.sub.27 H.sub.30 O.sub.3C: 80.56H:      7.51 n.sub.D.sup.18 1.554280.52 7.52      147 218     ##STR533##      ##STR534##      ##STR535##      a 92 C.sub.26 H.sub.30 O.sub.3C: 79.96H:      7.74 n.sub.D.sup.22 1.538579.94 7.83      148 219     ##STR536##      ##STR537##      ##STR538##      a 93 C.sub.27 H.sub.30 O.sub.3C: 80.56H:      7.51 n.sub.D.sup.19 1.5548 80.58 7.53      149 220     ##STR539##      ##STR540##      ##STR541##      a 90 C.sub.27 H.sub.32 O.sub.3C: 80.16H:      7.97 n.sub.D.sup.24 1.530280.21 8.04      150 221     ##STR542##      ##STR543##      ##STR544##      a 94 C.sub.28 H.sub.32 O.sub.3C: 80.73H:      7.74 n.sub.D.sup.20 1.532780.67 7.71      151 222     ##STR545##      ##STR546##      ##STR547##      a 82 C.sub.21 H.sub.21 O.sub.3 SClC: 64.85H:  5.44S:  8.25Cl: 9.12     n.sub.D.sup.20 1.537764.88 5.42 8.26 9.13      152 223     ##STR548##      ##STR549##      ##STR550##      a 77 C.sub.22 H.sub.21 O.sub.3 SFC: 68.73H:  5.51S:  8.34F:  4.94     n.sub.D.sup.20 1.546768.70 5.59 8.32 4.92      153 224     ##STR551##      ##STR552##      ##STR553##      a 86 C.sub.23 H.sub.24 O.sub.3 SC: 72.60H:  6.36S:  8.43 n.sub.D.sup.19     1.536672.54 6.33 8.50      154 225     ##STR554##      ##STR555##      ##STR556##      a 79 C.sub.23 H.sub.24 O.sub.3 SC: 72.60H:  6.36S:  8.43n.sub.D.sup.19     1.527772.61 6.38 8.49      155 226     ##STR557##      ##STR558##      ##STR559##      a 81 C.sub.26 H.sub.28      O.sub.2C: 81.62H: 10.01 n.sub.D.sup.20 1.523581.6610.03  156 227      ##STR560##      ##STR561##      ##STR562##      a 72 C.sub.26 H.sub.25 O.sub.3 NC: 78.17H:  6.31N:      3.51  n.sub.D.sup.20 1.562478.19 6.28 3.61      157 228     ##STR563##      ##STR564##      ##STR565##      a 83 C.sub.22 H.sub.21 O.sub.3 SClC: 65.90H:  5.28S:  8.00Cl:  8.84     n.sub.D.sup.19 1.543365.99 5.27 8.04 8.82      158 229     ##STR566##      ##STR567##      ##STR568##      a 85 C.sub.22 H.sub.21 O.sub.3 SClC: 65.90H:  5.28S:  8.00Cl:  8.84     n.sub.D.sup.19 1.543665.91 5.29 8.16 8.83      159 230     ##STR569##      ##STR570##      ##STR571##      a 90 C.sub.25 H.sub.25 O.sub.2 ClC: 76.42H:  6.41Cl:      9.02 n.sub.D.sup.20 1.532976.44 6.43 9.09      160 231     ##STR572##      ##STR573##      ##STR574##      a 74 C.sub.25 H.sub.22 O.sub.3 NClC: 71.51H  5.28N:  3.34Cl:  8.44     n.sub.D.sup.20 1.553371.54 5.30 3.31 8.46      161 232     ##STR575##      ##STR576##      ##STR577##      a 75 C.sub.27 H.sub.27 O.sub.3 NC: 78.42H:  6.58N:  3.39 n.sub.D.sup.     20 1.523978.44 6.61 3.44      162 233     ##STR578##      ##STR579##      ##STR580##      a 86 C.sub.25 H.sub.28 O.sub.3 SC: 73.49H:  6.91S:  7.85 n.sub.D.sup.20     1.556773.51 6.94 7.86      163 234     ##STR581##      ##STR582##      ##STR583##      a 89 C.sub.28 H.sub.32 O.sub.2C: 83.96H:      8.05 n.sub.D.sup.20 1.534183.99 8.06      164 235     ##STR584##      ##STR585##      ##STR586##      a 80 C.sub.28 H.sub.29 O.sub.3 NC: 78.66H:  6.84N:  3.28 n.sub.D.sup.20     1.522678.67 6.90 3.11      165 236     ##STR587##      ##STR588##      ##STR589##      a 79 C.sub.29 H.sub.31 O.sub.3 NC: 78.88H:  7.08N:  3.17 n.sub.D.sup.20     1.545178.79 7.06 3.24      166 237     ##STR590##      ##STR591##      ##STR592##      a 87 C.sub.24 H.sub.26 O.sub.3C: 79.53H:      7.23 n.sub.D.sup.20 1.533579.56 7.20      167 238     ##STR593##      ##STR594##      ##STR595##      a 89 C.sub.25 H.sub.25 O.sub.3 ClC: 73.43H:  6.16Cl:      8.67 n.sub.D.sup.19 1.542773.49 6.20 8.60      168 239     ##STR596##      ##STR597##      ##STR598##      a 89 C.sub.25 H.sub.28 O.sub.3C: 79.75H:      7.49 n.sub.D.sup.20 1.536679.72 7.52      169 240     ##STR599##      ##STR600##      ##STR601##      a 91 C.sub.26 H.sub.28 O.sub.3C: 80.38H:      7.26 n.sub.D.sup.21 1.522580.33 7.24      170 241     ##STR602##      ##STR603##      ##STR604##      a 76 C.sub.22 H.sub.24 O.sub.4C: 74.98H:      6.86 n.sub.D.sup.22 1.523675.02 6.80      171 242     ##STR605##      ##STR606##      ##STR607##      a 79 C.sub.22 H.sub.24 O.sub.3 SC: 71.71H:  6.56S:  8.70 n.sub.D.sup.20     1.547571.77 6.52 8.72      172 243     ##STR608##      ##STR609##      ##STR610##      a 79 C.sub.23 H.sub.24 O.sub.4C: 75.80H:      6.64 n.sub.D.sup.20  1.534475.76 6.62      173 244     ##STR611##      ##STR612##      ##STR613##      a 82 C.sub.21 H.sub.22 O.sub.3 SC: 71.15H:  6.26S:  9.04 n.sub.D.sup.19     1.522671.09 6.22 9.11      174 245 CH.sub.3     ##STR614##      ##STR615##      a 89 C.sub.20 H.sub.22 O.sub.3C: 77.37H:      7.14 N.sub.D.sup.28 1.529377.29 7.16  175 246 C.sub.2      H.sub.5     ##STR616##      ##STR617##      a 89 C.sub.21 H.sub.24 O.sub.3C: 77.75H:  7.46 n.sub.D.sup.24.5     1.527677.78 7.44      176 247     ##STR618##      ##STR619##      ##STR620##      a 86 C.sub.23 H.sub.26 O.sub.3C: 78.83H:      7.48 n.sub.D.sup.28 1.548378.81 7.40  177 248 C.sub.2      H.sub.5     ##STR621##      ##STR622##      a 90 C.sub.18 H.sub.22 O.sub.3C: 75.49H:  7.74 n.sub.D.sup.24.5     1.496575.53 7.69      178 249     ##STR623##      ##STR624##      ##STR625##      a 90 C.sub.22 H.sub.26 O.sub.3C: 78.07H:  7.74 n.sub.D.sup.24.5     1.524878.10 7.74      179 250     ##STR626##      ##STR627##      ##STR628##      a 85 C.sub.22 H.sub.28 O.sub.2C: 81.44H:      8.70n.sub.D.sup.28 1.561581.64 8.53      180 251     ##STR629##      ##STR630##      ##STR631##      a 91 C.sub.19 H.sub.25 O.sub.4 NC: 68.86H:  7.60N:  4.23 n.sub.D.sup.25     1.538068.69 7.64 4.10      181 252     ##STR632##      ##STR633##      ##STR634##      a 88 C.sub.17 H.sub.23 O.sub.4 NC: 66.86H:  7.59N:  4.59 n.sub.D.sup.25     1.523766.97 7.50 4.45      182 253     ##STR635##      ##STR636##      ##STR637##      a 90 C.sub.17 H.sub.17 O.sub.2 Cl.sub.5C: 47.42H:  3.98Cl:41.17     n.sub.D.sup.28 1.539547.88 3.7041.53      183 254     ##STR638##      ##STR639##      ##STR640##      a 85 C.sub.20 H.sub.22 O.sub.3C: 77.37H:  7.14 n.sub.D.sup.24.5     1.508877.35 7.17      184 255     ##STR641##      ##STR642##      ##STR643##      a 90 C.sub.21 H.sub.28 O.sub.2C: 80.73H:      9.03 n.sub.D.sup.25 1.513280.70 8.98      185 256     ##STR644##      ##STR645##      ##STR646##      a 89 C.sub.20 H.sub.25 O.sub.2 ClC: 72.16H:      7.59Cl:10.65 n.sub.D.sup.25 1.520572.05 7.5510.92      186 257     ##STR647##      ##STR648##      ##STR649##      a 86 C.sub.20 H.sub.28 O.sub.3C: 75.91H:  8.92 n.sub.D.sup.24.5     1.508575.86 8.90      187 258     ##STR650##      ##STR651##      ##STR652##      a 90 C.sub.23 H.sub.28 O.sub.2 SC: 74.96H:  7.66S:  8.70 n.sub.D.sup.23     1.537074.78 7.62 8.58      188 259     ##STR653##      ##STR654##      ##STR655##      a 89 C.sub.19 H.sub.26 O.sub.2 SC: 71.66H:  8.23S: 10.07 n.sub.D.sup.23     1.535271.69 8.24 9.80      189 260     ##STR656##      ##STR657##      ##STR658##      a 92 C.sub.19 H.sub.24 O.sub.2 SC: 72.11H:  7.64S: 10.13 n.sub.D.sup.23     1.532372.15 7.6810.05      190  261     ##STR659##      ##STR660##      ##STR661##      a 85 C.sub.25 H.sub.27 O.sub.3 NC: 77.09H:  6.99N:  3.60 n.sub.D.sup.28     1.548676.93 6.92 3.52      191 262     ##STR662##      ##STR663##      ##STR664##      a 86 C.sub.23 H.sub.28 O.sub.2C: 82.10H:      8.39 n.sub.D.sup.28 1.521382.15 8.39      192 263 CH.sub.3     ##STR665##      ##STR666##      a 86 C.sub.21 H.sub.24 O.sub.3C: 77.75H:      7.46 n.sub.D.sup.28 1.5309 77.60 7.48  193 264 C.sub.2      H.sub.5     ##STR667##      ##STR668##      a 88 C.sub.22 H.sub.26 O.sub.3C: 78.07H:      7.74 n.sub.D.sup.24 1.530878.12 7.61      194 265     ##STR669##      ##STR670##      ##STR671##      a 86 C.sub.24 H.sub.28 O.sub.3C: 79.09H:      7.74 n.sub.D.sup.24 1.546778.80 7.76  195 266 C.sub.2      H.sub.5     ##STR672##      ##STR673##      a 86 C.sub.19 H.sub.26 O.sub.3C: 75.46H:      8.67 n.sub.D.sup.28 1.508875.40 8.66      196 267     ##STR674##      ##STR675##      ##STR676##      a 90 C.sub.20 H.sub.26 O.sub.3C: 76.40H:  8.34 n.sub.D.sup.24.5     1.514076.58 8.29      197 268     ##STR677##      ##STR678##      ##STR679##      a 85 C.sub.21 H.sub.24 O.sub.3C: 77.75H:  7.46 n.sub. D.sup.24.5     1.513377.81 7.40      198 269     ##STR680##      ##STR681##      ##STR682##      a 87 C.sub.19 H.sub.24 O.sub.3C: 75.97H:  8.05 n.sub.D.sup.24.5     1.506475.86 8.04      199 270     ##STR683##      ##STR684##      ##STR685##      a 92 C.sub.22 H.sub.25 O.sub.3 ClC: 70.86H:  6.76Cl:      9.51 n.sub.D.sup.24.5 1.535870.66 6.73 9.30      200 271     ##STR686##      ##STR687##      ##STR688##      a 88 C.sub.19 H.sub.25 O.sub.2 ClSC: 64.66H:  7.14Cl: 10.05S:  9.09     n.sub.D.sup.23 1.543064.74 7.15 9.77 9.13      201 272     ##STR689##      ##STR690##      ##STR691##      a 90 C.sub.25 H.sub.30 O.sub. 3C: 79.33H:  7.99  n.sub.D.sup.23     1.547479.25 7.90      202 273     ##STR692##      ##STR693##      ##STR694##      a 87 C.sub.21 H.sub.30 O.sub.3C: 76.32H:      9.15 n.sub.D.sup.28 1.503076.55 9.13      203 274     ##STR695##      ##STR696##      ##STR697##      a 87 C.sub.25 H.sub.30 O.sub.3C : 79.33H :  7.99 n.sub.D.sup.28     1.524379.47 7.95      204 275     ##STR698##      ##STR699##      ##STR700##      a 89 C.sub.24 H.sub.28 O.sub.3C: 79.09H:      7.74 n.sub.D.sup.24 1.525279.05 7.73      205 276     ##STR701##      ##STR702##      ##STR703##      a 86 C.sub.21 H.sub.24 O.sub.3C: 77.75H:      7.46 n.sub.D.sup.24 1.5097 77.62 7.49      206 277     ##STR704##      ##STR705##      ##STR706##      a 89 C.sub.25 H.sub.27 O.sub.3 NC: 77.09H:  6.99N:      3.60  n.sub.D.sup.24 1.547077.11 6.80 3.53      207 278 CH.sub.3     ##STR707##      ##STR708##      a 89 C.sub.19 H.sub.20 O.sub.4 SC: 66.26H:  5.85S:  9.31 n.sub.D.sup.23     1.533566.07 5.88 9.24      208 279     ##STR709##      ##STR710##      ##STR711##      a 83 C.sub.23 H.sub.26 O.sub. 4C: 75.38H:  7.15  n.sub.D.sup.23     1.508875.15 7.02       209 280     ##STR712##      ##STR713##      ##STR714##      a 87 C.sub.23 H.sub.26 O.sub.4C: 75.38H:      7.15 n.sub.D.sup.23 1.507575.36 7.18  210  281 C.sub.2      H.sub.5     ##STR715##      ##STR716##      a 86 C.sub.20 H.sub.24 OC: 76.89H:  7.74 n.sub.D.sup.28.5 1.517876.54     7.70      211 282     ##STR717##      ##STR718##      ##STR719##      a 86 C.sub.21 H.sub.26 O.sub. 3C: 77.27H:      8.03 n.sub.D.sup.25 1.518577.34 8.06      212 283     ##STR720##      ##STR721##      ##STR722##      a 90 C.sub.22 H.sub.26 O.sub.3C: 78.07H:      7.74  n.sub.D.sup.25 1.541377.95 7.90      213 284     ##STR723##      ##STR724##      ##STR725##      a  89 C.sub.17 H.sub.22 O.sub.3C: 74.42H:      8.08 n.sub.D.sup.25 1.496074.85 8.15      214 285     ##STR726##      ##STR727##      ##STR728##      a 85 C.sub.23 H.sub.25 O.sub.3 NC: 76.01H:  6.93N:  3.85 n.sub.D.sup.25     1.540776.10 6.88      3.62 215 286 CH.sub.3     ##STR729##      ##STR730##      a 91 C.sub.19 H.sub.22 O.sub.3C: 76.48H:  7.43 n.sub.D.sup.28.5     1.520276.41 7.55  216 287 C.sub.2      H.sub.5     ##STR731##      ##STR732##      a 87 C.sub.20 H.sub.24 O.sub.3C: 76.89H:  7.74 n.sub.D.sup.28.5     1.516576.71 7.85      217 288     ##STR733##      ##STR734##      ##STR735##      a 88 C.sub.21 H.sub.26 O.sub.3C: 77.27H:      8.03 n.sub.D.sup.23 1.515377.25 8.09  218 289 C.sub.2      H.sub.5     ##STR736##      ##STR737##      a 88 C.sub.21 H.sub.26 O.sub.3C: 77.27H:      8.03 n.sub.D.sup.27 1.515077.45 8.01      219 290     ##STR738##      ##STR739##      ##STR740##      a 92 C.sub.22 H.sub.28 O.sub.3C: 77.61H:      8.29 n.sub.D.sup.27 1.513477.76 8.25      220  291     ##STR741##      ##STR742##      ##STR743##      a 89  C.sub.23 H.sub.28 O.sub.3C: 78.37H:      8.01 n.sub.D.sup.27 1.536378.43 8.08  221 292 CH.sub.2CHCH.sub.2      ##STR744##      ##STR745##      a 89  C.sub.23 H.sub.26 O.sub.3 C: 78.83H:  7.48 n.sub.D.sup.25     1.534578.85 7.48      222 293     ##STR746##      ##STR747##      ##STR748##      a 90  C.sub.23 H.sub.24 O.sub.3C: 79.28H:      6.94 n.sub.D.sup.25 1.536379.20 7.02      223 294     ##STR749##      ##STR750##      ##STR751##      a 86 C.sub.20 H.sub.26 O.sub.3C: 76.40H:      8.34 n.sub.D.sup.28 1.499576.49 8.55      224 295     ##STR752##      ##STR753##      ##STR754##      a 82 C.sub.24 H.sub.26 O.sub.3C: 79.53H:      7.23 n.sub.D.sup.22 1.535678.91 7.28  225 296 CH.sub.3      CH.sub.2     ##STR755##      ##STR756##      a 89 C.sub.22 H.sub.24 O.sub.2C: 82.46H:      7.55 n.sub.D.sup.19 1.523882.41 7.53  226 297  CH.sub.3 CH.sub.2      ##STR757##      ##STR758##      a 78 C.sub.19 H.sub.22 O.sub.3C: 76.48H:      7.43 n.sub.D.sup.20 1.554276.55 7.37      227 298     ##STR759##      ##STR760##      ##STR761##      a 84 C.sub.25 H.sub.26 O.sub.3 SC: 73.86H:  6.45S:  7.89 n.sub.D.sup.20     1.558773.92 6.40 7.81      228 299     ##STR762##      ##STR763##      ##STR764##      a 87  C.sub. 23 H.sub.24 O.sub.4C: 75.80H:  6.64 n.sub.D.sup.20     1.536675.77 6.72      229 300     ##STR765##      ##STR766##      ##STR767##      a 91 C.sub.23 H.sub.26 O.sub.3C: 78.82H:      7.48 n.sub.D.sup.20 1.541278.79      7.55

Most of the important intermediates of the present invention, i.e.,disubstituted acetic acid, can effectively be prepared in high yieldsvia one of the alternative procedures (A), (B) and (C) given below.##STR768## wherein Ar represents an aryl group, R' represents an alkyl,alkenyl or alkynyl group, R" represents hydrogen or a lower alkyl group,and R'" represents a lower alkyl group.

STEP 1

This procedure can be accomplished by alkylating the correspondingarylacetonitrile with an appropriate halide or sulfoxylate of theformula R'-X in an inert solvent (for example, ethers, tetrahydrofuran,benzene, toluene, etc. including liquid ammonia when NaNH₂ and the likeis used as a base described below) in the presence of a base such asalkali metals, alkali metal hydrides, alkali metal amides and the likeat room temperature or an elevated temperature.

STEP 2

This procedure can be accomplished under the well-known conditionscommonly used for hydrolysis of a nitrile group, i.e., by heating thenitrile with a mineral acid or an alkali hydroxide.

STEPS 3 AND 4

This procedure can be accomplished by alkylating the correspondingphenylacetic acid or a lower-alkyl ester thereof with an appropriatehalide or sulfoxylate of the formula R'--X in an inert solvent in thepresence of a base such as alkali metals or hydrides thereof, n-butyllithium and the like at room temperature or an elevated temperature,and, when the lower-alkyl ester is used for the alkylation, hydrolyzingthe resulting ester with an appropriate acid or alkali in the usualmanner.

STEP 5

This procedure can be accomplished by reacting an arylmalonic acid ester(which is easily obtainable by carbalkoxylation of the correspondingarylacetic ester) with an appropriate halide or sulfoxylate of theformula R'--X in the presence of an alkali metal alkoxide or an alkalimetal hydride as a base in an inert solvent or an alcohol correspondingto the alkali metal alkoxide.

STEP 6

This procedure can be accomplished under the well-known conditionscommonly used for hydrolysis of a usual ester, i.e., by hydrolyzing theester with an acid or alkali to obtain the corresponding dicarboxylicacid followed by heat-decarbonization to obtain the desired carboxylicacid, or can be accomplished by heating the diester with an alkali metalalkoxide in an alcohol whereby the diester is easily converted into amonoester by decarboxylation and hydrolyzing the monoester by thewell-known procedure to obtain the corresponding carboxylic acid in highyields.

The preparation of the intermediates, carboxylic acids, can beillustrated by the following Synthesis Examples, but they are not to beconstrued as limiting the processes or intermediates of the presentinvention.

SYNTHESIS EXAMPLE 1 α-Isopropyl-4-methoxyphenylacetonitrile

14.72 g (0.1 mole) of 4-methoxyphenylacetonitrile in 10 ml of drytoluene was added to a stirred solution of sodium hydride (2.64 g, 0.11mole) and isopropylbromide (18.45 g, 0.15 mole) in 100 ml of dry tolueneand 10 ml of dry dimethylformamide which was heated at 70° C, in 30minutes. After addition was completed, the mixture was heated at atemperature of from 80° to 85° C for 3 hours, and cooled to roomtemperature then poured into 200 g of ice-water.

Organic layer was separated and the aqueous layer was extracted withether twice. Combined organic layer was washed successively with waterand saturated sodium chloride solution, and dried over anhydrous sodiumsulfate. The solvent was removed in vacuo and the residual oil wasdistilled in vacuo to afford 15.70 g (b.p. 95°-96°/0.15 mmHg, 83.0%) ofα-isopropyl-4-methoxyphenylacetonitrile.

In similar manners, following α-isopropylphenylacetonitriles wereobtained.

    __________________________________________________________________________                                             Yield                                                               b.p.° C/mmHg                                                                     (%)                                  __________________________________________________________________________    4-bromo-α-isopropylphenyl-acetonitrile                                                             1)  90 - 93°/0.10                                                                    82.1                                 4-ethyl-d-isopropylphenyl-acetonitrile                                                                   2)  96 - 93°/0.10                                                                    85.1                                 4-isopropyl-α-isopropylphenyl-acetonitrile                                                         3)  100 - 102°/0.40                                                                  83.5                                 3-chloro-α-isopropylphenyl-acetonitrile                                                            4)  104 - 106°/0.30                                                                  80.2                                 4-fluoro-α-isopropylphenyl-acetonitrile                                                            5)  89 - 90°/5.0                                                                     80.7                                 3-fluoro-α-isopropylphenyl-acetonitrile                                                            6)  89 - 90°/5.0                                                                     81.1                                 4-thiomethyl-α-isopropylphenyl-acetonitrile                                                        7)  105°/0.10                                                                        75.1                                 2,4,6-trimethyl-α-isopropylphenyl-acetonitrile                                                     8)  87 - 88°/0.20                                                                    53.1                                 3-trifluoromethyl-α-isopropylphenyl-acetonitrile                                                   9)  95 - 96°/5.0                                                                     87.9                                 3.4-methylenedioxy-α-isopropylphenyl-acetonitrile                                                  10) 95 - 100°/0.2                                                                    78.2                                 3-phenoxy-α-isopropylphenyl-acetonitrile                                                           11) 147 -148°/0.3                                                                    85.2                                 __________________________________________________________________________     1) Starting 4-bromophenylacetonitrile was synthesized from 4-bromotoluene     which was brominated at 180° C with bromine and converted into         nitrile with potassium cyanide in DMSO--H.sub.2 O.                            2) Ethylbenzene was chloromethylated with Kosolopoff method (JACS, 68,        1670 (1946)) and the chloride was purified by fractional distillation,        then converted into nitrile in similar manner described above.                3) Isopropylbenzene was chloromethylated and converted into a nitrile.        4) Commercially available 3-chlorobenzylchloride was converted into a         nitrile similarly.                                                             5, 6) 3-fluorotoluene and 4-fluorotoluene were brominated with NBS in        carbon tetrachloride then converted into nitriles.                            7) Thioanisole was chloromethylated with paraformaldehyde and zinc            chloride in poor conversion, then converted into nitrile.                     8) Mesitylene was chloromethylated and converted into a nitrile. In this      case, alkylation proceeded very slowly even though an elevated temperatur     (110° C) and longer reaction times (15 hours) were tried.              9) 3-bromobenzotrifluoride was converted to                                   3-hydroxymethylbenzotrifluoride via Grignard method (R. Filler and H.         Novar, J.O.C., 25, 733 (1960)) and converted into a bromide (HBr--H.sub.2     SO.sub.4) and a nitrile (KCN--DMSO), successively.                            10) Piperonyl alcohol was converted into a chloride with thionyl chloride     at 0° C, followed by KCN/DMSO to afford the nitrile.                   11) m-phenoxytoluene which was obtained from m-cresol and bromotoluene wa     brominated at 230° C with bromine, and the corresponding bromide       was converted into a nitrile similarly.                                  

SYNTHESIS EXAMPLE 2 4-Bromo-α-isopropyl-phenylacetic acid

20 g of 4-bromo-α-isopropylphenylacetonitrile was heated with 140 ml ofsulfuric acid (50 V/V %) at 145° C for 6 hours. The cooled reactionmixture was poured onto 150 g of ice, and extracted with ether (100 ml ×3). The ether layers were combined and extracted with three 70 mlportions of cold 5% sodium hydroxide solution, and the aqueous extractswere acidified with concentrated hydrochloric acid, and then extractedwith ether. The ether extract was washed successively with water,saturated sodium chloride solution, dried over anhydrous sodium sulfate.Removal of the solvent gate 16.9 g (78.2%) of white crystals, which weresufficiently pure for use in next step. A portion of the crystals wasrecrystallized from benzene, melting point: 97°-98° C.

SYNTHESIS EXAMPLE 3 4-Methoxy-α-isopropylphenylacetic acid

12.8 g of 4-methoxy-α-isopropylphenylacetonitrile was heated underreflux (140° C) with 200 ml of ethylene-glycol and 40 g of 50% aqueouspotassium hydroxide solution for 8 hours. The cooled reaction mixturewas poured into 200 g of ice-water, which was washed with ether. Theaqueous layer was acidified with concentrated hydrochloric acid, andextracted with ether (150 ml × 3). The combined ether extract was washedsuccessively with water, saturated sodium chloride, then dried overanhydrous sodium sulfate. Removal of the solvent gave 11.30 g (80.4%) ofwhite crystals. The acid recrystallized from benzene melted at 146°-148°C.

In similar manners following acids were prepared.

    ______________________________________                                                   Method of                                                                     Hydro-         N.M.R. signals                                                 lysis  Yields  (CHCl.sub.3, in ppm)                                ______________________________________                                        3-trifluoromethyl-            0.74 (3H, d.J = 7Hz),                           α-isopropyl-phenyl-                                                                  A        25.0    1.07 (3H, d.J = 7Hz),                           acetic acid                   1.9 - 2.6 (1H, m.),                                                           3.22 (1H, d.J = 10Hz),                                                        7.4 - 7.7 (4H, m.),                                                           10.6 (1H, b.S)                                  4-fluoro-α-isopropyl-   0.69 (3H, d.J = 7Hz),                           phenylacetic acid                                                                          A        85.2    1.05 (3H, d.J = 7Hz),                                                         1.9 - 2.6 (1H, m.)                                                            3.10 (1H, d.J = 12Hz),                                                        6.9 - 7.4 (4H, m.),                                                           9.70 (1H, b.S.)                                 4-thiomethyl-α-         0.69 (3H, d.J = 6.5Hz),                         isopropyl-phenyl-                                                                          B        78.2    1.07 (3H, d.J = 6.5Hz),                         acetic acid                   2.42 (3H, S),                                                                 3.07 (1H, d.J = 10Hz),                                                        7.19 (4H, S.),                                                                9.64 (1H, b.S.)                                 2,4,6-trimethyl-α-      0.61 (3H, d.J = 7Hz),                           isopropyl-phenyl-                                                                          A        34.5    1.15 (3H, d.J = 7Hz),                           acetic acid                   1.22 (3H, S.),                                                                1.32 (6H, S.),                                                                2.25 - 2.95 (1H, m.),                                                         3.68 (1H, d.J = 10Hz),                                                        6.82 (2H, b.S.),                                                              9.50 (1H, b.S.)                                 3-methoxy-α-isopropyl-  0.65 (3H, S.J = 7Hz),                           phenylacetic acid                                                                          B        87.2    1.05 (3H, S.J = 7Hz),                                                         1.7 - 2.6 (1H, m.),                                                           3.07 (1H, d.J = 11hz),                                                        3.75 (3H, S.),                                                                6.5 - 7.1 (4H, m.),                                                           6.2 (1H, b.S.)                                  4-methyl-α-isopropyl-   0.68 (3H, d.J = 7Hz),                           phenylacetic acid                                                                          A        88.2    1.05 (3H, d.J = 7Hz),                                                         1.95 - 2.50 (1H, m.),                                                         2.29 (3H, S.),                                                                3.05 (1H, d.J = 11Hz),                                                        7.11 (centered, 4H,                                                           AB type 8),                                                                   9.52 (1H, b.S.)                                 ______________________________________                                         * Signal patterns were designated as follows. S: signlet, d: doublet, m:      multiplet, bS: broad Singlet                                                  * Hydrolysis Method A: 50% H.sub.2 SO.sub.4, Method B:                        Ethyleneglycolaqueous KOH                                                

SYNTHESIS EXAMPLE 4 Diethyl-2-phenyl-2-allyl-malonate

Diethyl-2-phenylmalonate (23.60 g, 0.10 mole, prepared fromethylphenylacetate, Org. Synth. Call, Vol. 2, 288) in 20 ml of drybenzene was added to a stirred solution of sodium hydride (2.38 g, 0.12mole) in 150 ml of dry benzene at 30°-40° C, and the mixture was kept at40° C for 30 minutes. To the white enolate generated was added asolution of allyl bromide (24.2 g, 0.10 mole) in 20 ml of dry benzene at5° C, thereafter stirring continued at room temperature for one hour.

The reaction mixture was poured into 200 ml of ice-water, and theorganic layer was separated. The aqueous layer was extracted with ether(two 100 ml portions). The organic layers were combined, and washedsuccessively with 5% hydrochloric acid, water and saturated sodiumchloride solution, then dried over anhydrous sodium sulfate. The solventwas removed in vacuo, and the residual oil was distilled at reducedpressure to afford 24.27 g (87.90%, b.p. 115°-120°/0.25 mmHg) ofdiethyl-2-phenyl-2-allyl-malonate.

SYNTHESIS EXAMPLE 5 Ethyl-α-allylphenylacetate

Diethyl allylphenyl malonate (20.0 g, 0.072 mole) in 250 ml of dry EtOHwas heated under reflux with 7.4 g of sodium ethoxide for 5 hours.

Ethanol was removed in vacuo, and the residue was poured to 75 g ofice-water. The mixture was extracted with ether (three 50 ml portions),ether layer was washed with saturated sodium chloride solution, driedover anhydrous sodium sulfate. Removal of the solvent, and distillationat reduced pressures afforded 12.54 g (b.p. 60°-63°/0.13 mmHg, 85.3%) ofthe phenyl acetate.

SYNTHESIS EXAMPLE 6 α-Allyl-phenyl acetic acid

Above ethylester was hydrolyzed with 10% potassium hydroxide in methanolat room temperature in a usual manner to give the acid (yield 94.6%,m.p. 34° C).

SYNTHESIS EXAMPLE 7 Diethyl-2-phenyl-2-propargyl malonate

In a similar manner to Example 4, the malonate was prepared in 81.7%yield (b.p. 115°-120°/0.15 mmHg).

SYNTHESIS EXAMPLE 8 α-Propargyl phenyl acetic acid

20.0 g (0.073 mole) of diethyl-2-phenyl-2-propargyl malonate washydrolyzed in 330 g of 5% methanolic potassium hydroxide at refluxtemperature for 2 hours. Methanol was removed in vacuo, and the residuewas dissolved in 150 ml of cold water, acidification with concentratedHCl caused a spontaneous decarboxylation to give the monocarboxylicacid, which was collected by ether extraction. (12.4 g, 97.6%, m.p.90°-93° C).

SYNTHESIS EXAMPLE 9

Although the compound which bears an isopropyl group on α-position suchas compounds No. 83, No. 85, No. 125, can be prepared in the usualesterification method using corresponding acid chloride, the double bondof the isopropenyl group readily isomerized to α-β position to make theacid or acid chloride into a mixture of double bond positions. A lowyield was attained after chromatographic purification.

Following routes seemed to be better than the usual methods.

3'-Phenoxybenzyl-α-isopropenyl-4-methoxyphenylacetate (Compound No. 82)

1. To a solution of isopropylmagnesium bromide, which was prepared from38.1 g of isopropylbromide and 7.3 g of magnesium in 90 ml of dry ether,was added a solution of 4-methoxyphenylacetic acid (16.6 g) in 100 ml ofdry tetrahydrofuran at an ice-bath temperature, thereafter the solutionwas stirred at room temperature for 2 hours. Dry acetone (7.0 g),diluted with 20 ml of dry toluene, was added to the solution, and it washeated to reflux for 5 hours. Cooled solution was acidified with 15%sulfuric acid, the aqueous phase separated, which was extracted withether. Combined organic layers were extracted with 10% sodium carbonatesolution. Carbonate extracted was acidified with concentratedhydrochloric acid and extracted with ether. Ether extract was dried overanhydrous sodium sulfate. Removement of the solvent and arecrystallization from ethyl acetate afforded 12.4 g of4-methoxy-β,β-dimethylatropic acid (55.2%, m.p. 124°-125° C).

2. To a solution of 4-methoxy-β,β-dimethylatropic acid (5.0 g) andtriethylamine (4.5 g) in 50 ml of dimethylformamide, was added 7.0 g of3-phenoxybenzylbromide gradually at an ice-bath temperature, and stirredovernight at room temperature. The mixture was poured into cold 10% H₂SO₄ and extracted with ether. The ether layer was washed with 10% sodiumcarbonate solution and dried over anhydrous sodium sulfate. Removementof the solvent gave 4.8 g of crude hydroxyester, which was dehydratedwith P₂ O₅ in benzene at 80° C for 13 hours. Filtration, and removementof the solvent gave crude isopropenyl-ester as a dark oil. Purificationwith silica-gel chromatography afforded 1.9 g of pure ester. (40.5%,n_(D) ¹⁶ 1.5798)

SYNTHESIS EXAMPLE 10 Ethyl-2-(cyclohexane-1'-ol-1'-yl)butyrate

This was prepared from ethyl-2-bromobutyrate (29.3 g), cyclohexanone(14.7 g) and zinc (9.51 g) in benzene (50 ml) and toluene (25 ml) underusual Reformatsky conditions (b.p. 166°-117°/4 mmHg, yield 16.4 g,51.0%).

SYNTHESIS EXAMPLE 11 Ethyl-2-(cyclohexene-1-yl)-butyrate

Above hydroxyester (16.4 g) was heated under reflux with phosphoruspentoxide (11 g) in 60 ml of dry benzene for 3 hours. Cooled mixture waspoured onto 80 ml of cold water, organic layer was separated and washedwith saturated sodium chloride solution. Solvent was removed in vacuo,and the residue was distilled under reduced pressure to afford 11.6 g ofpale yellow oil. (76.5%, b.p. 88°-92°/4 mmHg)

SYNTHESIS EXAMPLE 12 Ethyl-2,3-diethyl-3-hydroxy-pentanoate

In similar manners described in Example 10, this was prepared from3-pentanone and ethyl-2-bromobutyrate. (yield 52.8%, b.p. 113°-121°/20mmHg)

SYNTHESIS EXAMPLE 13

The hydroxyester obtained in Example 12, was dehydrolyzed withphosphorous pentoxide in benzene in a manner described above. (yield68.2%, b.p. 95°-98°/22 mmHg)

The compounds of the type designated as Compound Nos. 18, 21, 245, 246and 248 were prepared from the corresponding carboxylic acid or an acidchloride derived therefrom which is obtained by hydrolyzing the ethylester prepared in the similar manner as described in Synthesis Examples10-13. The hydrolysis can be effected by the conventional procedureusing sodium hydroxide or potassium hydroxide in methanol at roomtemperature. The carboxylic acid thus obtained was found to contain asmall amount of isomers with respect to double bonds (up to about 10%),but the crude carboxylic acid was subjected to esterifications withoutisolating impurities (isomers) and the product was purified by silicagel chromatography in the final step.

The substituted ester compounds represented by the formula (I) exhibitan excellent pesticidal activity and are expected to have a repellingactivity against mites as well as a synergestic activity with otherbiologically active agents, and can be employed in a wide variety ofapplications at low cost as pesticidal compositions for use inagricultural and horticultural, forest, sanitary fields as well as in astockroom of cereals and a composition for controlling mites.

In practical use of these compounds, an appropriate amount of one ormore solvents, fillers, diluents, active agents, dispersing agents,surface active agents, spreaders, pressure-imparting agents, emulsifyingagents and attractants can be incorporated into the ester compounds ofthis invention to form an emulsifiable concentrate, a wettable powder, adust, a granule, a fine grain, a coating agent, a powder, an oilpreparation, an aerosol, a mosquito coil, a smoking agent, a fumigatingagent, a mosquito insence agent for electrical vaporization, and thelike.

The effect of the pesticidal compositions of this invention is furtherillustrated by the following Experiments.

EXPERIMENTAL EXAMPLE 1

An emulsifiable concentrate was prepared by blending each of thecompounds (1) to (300) of the present invention, xylol and Sorpol SM-200(trade name; manufactured by Toho Chemical Co., Ltd.) in a proportion of25%, 50% and 25% (by weight), respectively. 20 to 25 day-old rice plantsafter seeding were grown in pots and sprayed with each 300-fold dilutesolution of the emulsifiable concentrates thus prepared and a 300-folddilute solution of carbaryl 30% wettable powder diluted with water as acontrol commercial agent in an amount of 10 ml/pot in each case and thenthe pots were covered by a cylindrical metal net. 15 small brownplanthoppers (Delphacodes striatella Fallen) per group were released ineach of the pots treated with carbaryl wettable powder, and compound (1)to (21) and (102) to (110), while 15 green rice leafhopper (Nephotettixbipuntatus cincticeps Uhler) per group were released in each of the potstreated with the carbaryl wettable powder and compounds (22) to (101)and (111) to (300). Observation on survival one day after the tretmentrevealed that each of the compounds of this invention exhibits more than90% killing effect as in the case of carbaryl.

EXPERIMENTAL EXAMPLE 2

Of the emulsifiable concentrates prepared in Experimental Example 1,each of those prepared from the compounds of Table 1 below was dilutedwith water to each of test concentrations and a 200 ml portion thereofwas added to a 300 ml volume beaker. 30 larvae of mosquito per groupwere released in each of the beaker and allowed to stand for 1 day.Survival was observed and a LC₅₀ (50% lethal concentration) wasdetermined by calculating a percent killing in each case. The resultsobtained are also shown in Table 1. As a control, lindane emulsifiableconcentrate was used.

                  Table 1                                                         ______________________________________                                        Insecticidal Activity on Larvae of                                            Mosquito (Culex pipiens)                                                      Test Emulsifiable                                                                         LC.sub.50                                                                              Test Emulsifiable                                                                           LC.sub.50                                  Concentrate (ppm)    Concentrate   (ppm)                                      ______________________________________                                        Com-   (1)      0.0015   Com-   (2)    0.0034                                 pound  (10)     0.0030   pound  (14)   0.0026                                 "      (16)     0.0014   "      (102)  0.0095                                 "      (103)    0.0092   "      (104)  0.0120                                 "      (105)    0.0105   "      (110)  0.0125                                 "      (111)    0.0025   "      (112)  0.0046                                 "      (113)    0.0053   "      (115)  0.0050                                 "      (119)    0.0044   "      (120)  0.0040                                 "      (121)    0.0037   "      (125)  0.0032                                 "      (126)    0.0056   "      (128)  0.0047                                 "      (145)    0.0039   "      (165)  0.0012                                 "      (167)    0.0043   "      (177)  0.0074                                 "      (180)    0.0072   "      (181)  0.0820                                 "      (183)    0.0885   "      (184)  0.0078                                 "      (204)    0.0075   "      (206)  0.0032                                 "      (210)    0.0035   "      (212)  0.0037                                 "      (214)    0.0127   "      (215)  0.0132                                 "      (226)    0.0135   "      (227)  0.0019                                 "      (231)    0.0014   "      (298)  0.0097                                 Lindane         0.22                                                          ______________________________________                                    

EXPERIMENTAL EXAMPLE 3

A 2000-fold dilute solution of each of the emulsifiable concentratesprepared in Experimental Example 1 from the compounds of Table 2 belowwas sprayed on a 12 day-oil seedling of mottled kidney beans afterseeding grown in a pot in an amount of 10 ml/pot. The seedling thustreated was cut off and put in a wide opening bottle. In the samemanner, an untreated seedling of mottled kidney beans in the same stagewas cut off and put in another wide opening bottle. Another freshseedling was fixed with pins bridging on the former treated seedling andthe latter untreated seedling. A leaf of mottled kidney beans on which anumber of spider mites (Tetranychus telarius) were parasitic was placedon the middle of the bridging seedling and allowed to stand for 2 days.Activity on repellency was assessed by investigating the numbers ofmites swarming on the treated seedling and the untreated seedling. Theassessment standards are as follows:

    ______________________________________                                        - :  The ratio of the number of mites on                                                                    1 : 1                                                the untreated seedling to that on the                                         treated seedling                                                         + :  "                        up to 4 : 1                                     ++ : "                        greater than                                                                  4 : 1                                           The results obtained was shown in Table 2 below.                              Table 2                                                                       Repellent Activity on Spider Mites                                            Test Emulsifiable     Test Emulsifiable                                       Concentrate Repellency                                                                              Concentrate  Repellency                                 ______________________________________                                        Com-   (1)      ++        Com-   (3)   +                                      pound  (4)      ++        pound  (10)  ++                                     "      (18)     +         "      (23)  +                                      "      (29)     ++        "      (35)  +                                      "      (45)     ++        "      (65)  +                                      "      (73)     +         "      (82)  ++                                     "      (92)     ++        "      (98)  ++                                     "      (116)    ++        "      (117) ++                                     "      (118)    ++        "      (121) ++                                     "      (124)    +         "      (127) ++                                     "      (130)    +         "      (165) ++                                     "      (168)    ++        "      (175) ++                                     "      (176)    ++        "      (177) ++                                     "      (178)    ++        "      (200) ++                                     "      (204)    ++        "      (206) ++                                     "      (210)    ++        "      (216) ++                                     "      (217)    ++        "      (218) ++                                     "      (219)    ++        "      (220) ++                                     "      (221)    ++        "      (227) ++                                     "      (234)    ++        "      (235) ++                                     ______________________________________                                    

EXPERIMENTAL EXAMPLE 4

0.2% oil preparation was prepared from each of the compounds (1), (2),(8), (14), (22), (25), (26), (27), (51), (62), (73), (82), (86), (88),to (90), (92), (94), (96), (111), (119), (121), (165), (175), (180),(184), (185), (195), (200), (201), and (208) and allethrin as a controlusing deodorized kerosene. About 50 adult mosquitoes (Culex pipiens)were released in a (70 Cm)³ volume glass box and sprayed with each ofthe oil preparations obtained above in an amount of 0.7 ml under apressure of 1.5 Kg/cm². It was found that more than 80% of mosquitoeswas knocked down by both allethrin and the compounds of this invention.

EXPERIMENTAL EXAMPLE 5

20 oriental house flies per group were released in a (70 cm)³ volumeglass box and sprayed with each of the oil preparations prepared inExperimental Example 4 from the compounds of Table 3 below and allethrinin an amount of 0.7 ml under a pressure of 1.5 Kg/cm². The test wasrepeated several times and the knock down of the flies was observed todetermine KT₅₀ (50% knock-down time). The results obtained are shown inTable 3.

                  Table 3                                                         ______________________________________                                        Activity on Knock-Down Against Oriental                                       House Flies                                                                   Test Oil     KT.sub.50                                                                              Test Oil       KT.sub.50                                Preparation  (sec.)   Preparation    (sec.)                                   ______________________________________                                        Com-   (1)       167      Com-   (8)     128                                  pound  (22)      136      pound  (51)    104                                  "      (62)      154      "      (63)    140                                  "      (82)      132      "      (88)    147                                  "      (89)      155      "      (96)     92                                  "      (111)     138      "      (119)   132                                  "      (121)     130      "      (165)   145                                  "      (175)     152      "      (180)   157                                  "      (184)     142      "      (185)   137                                  "      (195)     140      "      (200)   114                                  "      (201)     105      "      (208)   150                                  Allethrin        186                                                          ______________________________________                                    

EXPERIMENTAL EXAMPLE 6

To each of the compounds (22), (51), (62), (63), (82), (86), (125),(150), (160), (176), (177), (178), (184), (185), (191), (195), (200),(201), (204), (208), (210), (212) and (226) was added piperonyl butoxidein an amount of 5 times that of the active ingredient, respectively toprepare an acetone solution having a given concentration. Each of thethus prepared acetone solutions was applied onto a thoracic dosal plateof oriental house flies using a microshringe to observe a synergesticeffect on insecticidal activity by piperonyl butoxide. Potentiationmagnification of insecticidal activity by the addition of piperonylbutoxide is shown in Table 4.

                  Table 4                                                         ______________________________________                                        Potentiation Effect on Insecticidal                                           Activity by the Addition of Piperonyl                                         Butoxide                                                                                  Potenti-               Potenti-                                               ation                  ation                                                  magnifi-               Magnifi-                                   Test Compound                                                                             cation   TEst Compound cation                                     ______________________________________                                        Compound                                                                              (22)    5.0      Compound                                                                              (51)  7.2                                    "       (62)    5.3      "       (63)  4.8                                    "       (82)    6.7      "       (86)  4.5                                    "       (119)   5.5      "       (125) 6.0                                    "       (150)   4.2      "       (160) 7.2                                    "       (176)   5.2      "       (177) 5.8                                    "       (178)   5.4      "       (184) 5.6                                    "       (185)   5.0      "       (191) 4.3                                    "       (195)   5.7      "       (200) 7.5                                    "       (201)   7.0      "       (204) 4.7                                    "       (206)   5.1      "       (208) 5.2                                    "       (210)   4.8      "       (212) 5.0                                    "       (226)   4.5                                                           ______________________________________                                    

As is apparent from the above Experimental Examples, the compounds ofthis invention exhibit an excellent biological activity on variousnoxious insects and mites and also are of low toxicity.

Oral toxicity to mice for representative compounds is shown in the Tablebelow.

                  Table                                                           ______________________________________                                                    LD.sub.50              LD.sub.50                                  Test Compound                                                                             (mg/Kg)  Test Compound (mg/Kg)                                    ______________________________________                                        Compound                                                                              (1)     >1000    Compound                                                                              (2)   >1000                                  "       (8)       750    "       (22)    900                                  "       (62)    >1000    "       (63)  >1000                                  "       (80)    >2000    "       (82)  >1000                                  "       (108)   >1000    "       (119) >1000                                  "       (125)    1000    "       (129) >1000                                  "       (130)   >1000    "       (145) >1000                                  "       (150)   >1000    "       (176) >1000                                  "       (184)     940    "       (206) >1000                                  ______________________________________                                    

The compositions according to the present invention are very useful forcontrolling insanitary insects such as mosquitoes, flies andcockroaches, grain insects such as rice weevil (Calandra oryzae) andmites as well as agricultural noxious insects such as plant-hoppers,green rice leafhopper (Nephotettix bipuntatus cinticeps Uhler), cabbagearmy worms (Barathra brassicae Linne), diamond-back moths (Plutellamaculipennis Curtis), noctuidae, cabbage worm (Pieris rapae Linne), ricestem boress (Chilo suppressalis Walker), aphids, tortrixes, leaf-minersand the like.

They are also superior whenever they may be freely used for harvestedcrops, horticultural application, cultures in green house, and packagingmaterials for foodstuffs.

In preparing the compositions according to the present invention, it ispossible to obtain more excellent controlling effects by employing acombination of two or more compounds of this invention, and further, itis possible to obtain various compositions which are useful for a widevariety of applications by combining one or more compounds of thisinvention with other pesticidal compounds, for example, organochloriccompounds such as DDT, BHC, Methoxychlor and the like; organicphosphorus compounds such as Sumithion (trade name of Sumitomo ChemicalCompany Limited), DDVP, diazinon, phenthion, Cyanox (trade name ofSumitomo Chemical Company Limited) and the like; carbamates such as1-naphthyl-N-methylcarbamate, 3,4-dimethylphenyl N-methylcarbamate,3,5-dimethylphenyl N-methylcarbamate and the like;cyclopropanecarboxylic acid esters such pyrethrin, allethrin, Neopynamin(trade name of Sumitomo Chemical Company Limited), Chrysron (trade nameof Sumitomo Chemical Company Limited), 3-phenoxybenzyl chrysanthemate,5-propargylfurfuryl chrysanthemate and their geometrical or opticalisomers and the like, as well as piperonyl butoxide, sulfoxide,safroxane, isobornyl thiocyano acetate (I.B.T.A.) and octachlorodipropyl ester (S-421) which potentiate the effect of the esterssynergetically; terephthalic acid, isophthalic acid and BHT which aregenerally used in fumigating preparations; phenol derivatives used as astabilizer; bisphenol derivatives; arylamines such asphenyl-α-naphthylamine, phenyl-β-naphthylamine, a condensate ofphenetidin and acetone and the like; other insecticidal agents ormiticidal agnets such as Padan, Galecron, antimicrobial agents,nematocidal agents, herbicidal agents, fertilizers and otheragricultural agents. These compositions are expected to be useful forsaving man power for application of these agricultural agents and forobtaining synergetic activities between the active ingredients of thecomposition.

The preparation of compositions and the effect of compounds of thisinvention are further illustrated by the following Formulations andExamples, but they are not to be construed as limiting the scope of thisinvention. The parts used in formulations are by weight unless otherwiseindicated.

Formulation 1

To 20 parts of each of Compound Nos. 1 to 110 of this invention, therewere added 10 parts of Sumithion (as described previously), 10 parts ofSorpol SM-200 (as described previously), 60 parts of xylol, and themixture was dissolved by thoroughly stirring and mixing to obtain anemulsifiable concentrate in each case.

Formulation 2

To 10 parts of each of Compound Nos. 111 to 192 of this invention, therewere added 10 parts of Cyanox (as described previously), 10 parts ofSorpol SM-200 (as described previously) and 70 parts of xylol, and themixture was dissolved by thoroughly stirring and mixing to obtain anemulsifiable concentrate in each case.

Formulation 3

To 15 parts of each of Compound Nos. 193 to 232 of this invention, therewere added 30 parts of piperonyl butoxide, 15 parts of Sorpol SM-200 (asdescribed previously) and 40 parts of xylol, and the mixture wasdissolved by thoroughly stirring and mixing to obtain an emulsifiableconcentrate in each case.

Formulation 4

To 15 parts of each of Compound Nos. 233 to 300 of this invention, therewere added 20 parts of a 25% pyrethrin extract, 20 parts of piperonylbutoxide, 15 parts of Sorpol SM-200 (as described previously) and 30parts of xylol, and the mixture was dissolved by thoroughly stirring andmixing to obtain an emulsifiable concentrate in each case.

Formulation 5

0.05 parts of each of Compound Nos. 1, 10, 102, 103, 108 and 111 to 115was dissolved in kerosene in an amount sufficient to make 100 partsthereby obtaining an oil preparation in each case.

Formulation 6

To 0.02 parts of each Compound Nos. 116 and 192 of this invention, therewere added 0.1 parts of allethrin α-trans chrysanthemate and 1.5 partsof safroxane, and the mixture was dissolved in kerosene to prepare 100parts of an oil preparation in each case.

Formulation 7

To 0.02 parts of each of Compound Nos. 193 to 300 of this invention,there were added 0.1 parts of Neopynamine and 1.5 parts of S-421, andthe mixture was dissolved in kerosene to prepare 100 parts of an oilpreparation in each case.

Formulation 8

To 10 parts of each Compound Nos. 1 to 110 of this invention, there wereadded 10 parts of 1-naphthyl-N-methyl-carbamate and 5 parts of SorpolSM-200 (as described previously) followed by mixing. 75 parts of300-mesh talc was then added to the mixture and the resulting blend wasthoroughly stirred in a triturator to obtain an wettable powder in eachcase.

Formulation 9

The active pesticidal ingredients having a composition shown in Tablebelow were dissolved in 20 ml of methanol and the resulting solution wasmixed with 100 g of a carrier for mosquito coil (a mixture of tabupowder, pyrethrum marc and wood powder in a proportion of 3:5:1,respectively), followed by blending uniformly. After methanol wasevaporated, 150 ml of water was added to the blend, and the mixture wasthoroughly kneaded, molded and dried to prepare a mosquito coil in eachcase.

    ______________________________________                                        Formulations of Mosquito Coil                                                 No.       Composition                                                         ______________________________________                                        1.      Compound No. 1          0.3 g                                                 Allethrin               0.3 g                                         2.      Compound No. 8          0.3 g                                                 Allethrin               0.3 g                                         3.      Compound No. 22         0.3 g                                                 Allethrin               0.2 g                                                 BHT                     0.3 g                                         4.      Compound No. 37         0.3 g                                                 Allethrin               0.3 g                                         5.      Compound No. 51         0.3 g                                                 Allethrin α-trans chrysanthemate                                                                0.1 g                                                 BHT                     0.4 g                                         6.      Compound No. 62         0.2 g                                                 5-Propargylfurfuryl chrysanthe-                                               mate                    0.2 g                                                 BHT                     0.8 g                                         7.      Compound No. 82         0.3 g                                                 5-Propargyl-2-methyl-3-furylmethyl                                            chrysanthemate          0.1 g                                                 BHT                     0.4 g                                         8.      Compound No. 146        0.3 g                                                 Allethrin d-cis,trans chrysanthe-                                             mate                    0.1 g                                                 BHT                     0.5 g                                         9.      Compound No. 169        0.3 g                                                 Allethrin               0.2 g                                                 BHT                     0.5 g                                         10.     Compound No. 184        0.3 g                                                 Allethrin               0.3 g                                                 BHT                     0.3 g                                         ______________________________________                                    

Formulation 10

The active pesticidal ingredients having a composition shown in Tablebelow were dissolved in a mixed solvent comprising xylol and refinedkerosene (1:1 by volume) to prepare 15 parts of solution and thesolution was filled in an aerosol dispensing container. After a valvewas mounted to the container, the aerosol dispenser was pressurized bycharging 85 parts of a propellant (for example, freon, vinyl chloridemonomer, luquified petroleum gas, etc.) to obtain an aerosolpreparations.

    ______________________________________                                        Aerosol Formulations                                                          No.       Composition                                                         ______________________________________                                        1.      Compound No. 22       0.3 (part)                                              3-Phenoxybenzyl-d-cis,trans                                                   chrysanthemate        0.1                                             2.      Compound No. 22       0.2                                                     Neopynamin            0.2                                                     I.B.T.A.              1                                               3.      Compound No. 62       0.2                                                     Allethrin d-trans chrysanthemate                                                                    0.2                                                     Safroxane             2                                               4.      Compound No. 62       0.3                                                     DDVP                  0.3                                             5.      Compound No. 82       0.2                                                     Sumiothin             0.3                                                     Neopynamin            0.2                                             6.      Compound No. 82       0.4                                                     Piperonyl butoxide    2.0                                             7.      Compound No. 88       0.2                                                     Neopynamin            0.2                                                     Chrysron              0.1                                             8.      Compound No. 89       0.3                                                     Allethrin d-trans chrysanthemate                                                                    0.2                                             9.      Compound No. 96       0.2 (part)                                              Allethrin d-cis, trans                                                        chrysanthemate        0.2                                                     Safroxane             2                                               10.     Compound No. 102      0.4                                                     Neopynamin            0.1                                                     Piperonyl butoxide    1.5                                             11.     Compound No. 103      0.4                                                     Allethrin             0.1                                                     S-421                 1.5                                             12.     Compound No. 108      0.4                                                     25% Pyrethrin extract 0.5                                                     Piperonyl butoxide    1.0                                             13.     Compound No. 125      0.4                                                     I.B.T.A.              2                                               ______________________________________                                    

Formulation 11

The active pesticidal ingredients having a composition shown in Tablebelow were dissolved in an appropriate amount of chloroform, and thesolution was adsorbed uniformly on the surface of asbestos having a sizeof 2.5 cm × 1.5 cm and a thickness of 0.3 mm. Another piece of asbestoshaving the same size and thickness was then placed on the treatedsurface of the above asbestos to prepare a fibrous fumigation pesticidalcomposition (mat) for heating on a hot plate. As a fibrous carrier,those having the same effect as that of asbestos such as a pulp board,etc. may also be used in place of asbestos.

    ______________________________________                                        Formulation of Mat for Heating on Hot Plate                                   No.      Composition                                                          ______________________________________                                        1.       Compound No. 51        0.05 g                                                 Allethrin              0.02 g                                                 Piperonyl butoxide     0.07 g                                        2.       Compound No. 63        0.07 g                                                 Allethrin d-trans chrysanthemate                                                                     0.01 g                                                 Piperonyl butoxide     0.1 g                                         3.       Compound No. 80        0.5 g                                                  5-Propargyl furylmethyl                                                       chrysanthemate         0.02 g                                                 Piperonyl butoxide     0.15 g                                                 BHT                    0.1 g                                         4.       Compound No. 82        0.04 g                                                 Allethrin              0.04 g                                                 Piperonyl butoxide     0.08 g                                                 BHT                    0.1 g                                         5.       Compound No. 88        0.05 g                                                 5-Propargyla-2-methyl-3-furyl-                                                methyl chrysanthemate  0.02 g                                                 Piperonyl butoxide     0.15 g                                        6.       Compound No. 103       0.05 g                                                 Allethrin              0.02 g                                                 Piperonyl butoxide     0.15 g                                        7.       Compound No. 107       0.05 g                                                 5-Phenoxybenzyl chrysanthemate                                                                       0.03 g                                        8.       Compound No. 125       0.05 g                                                 Allethrin              0.01 g                                        ______________________________________                                    

Formulation 12

To 1 part of each of Compound Nos. 22, 51, 62, 63, 83, 86, 94, 103, 108and 125 of this invention was added 5 parts of piperonyl butoxide andthe mixture was dissolved in 20 parts of acetone. After 94 parts of300-mesh diatomaceous earth was added, the resulting blend wasthoroughly stirred and mixed in a triturator, and acetone was removed byevaporation to obtain a powder in each case.

EXAMPLE 1

10 third inster larvae of tabacco cutworm (Spodoptera lituna Fabricius)were placed in a glass tray having a high side-wall and a diameter of 14cm, and 1 ml of a 200-fold dilute solution of each of the emulsifiableconcentrates obtained in Formulations 1 to 3 diluted with water wassprayed on the larvae by a sprayer and the larvae thus treated were thentransferred into a glass tray containing feeds followed by allowing tostand. Two days after the treatment, greater than 80% of the larvae wasfound to be killed in each case.

EXAMPLE 2

In an area of the radish field in 5-6 leaf stage, a number of greenpeach aphid (Myzus persicae Sulza) was atomized with a 200-fold dilutesolution of each of the emulsifiable concentrates obtained inFormulations 1, 2 and 4 diluted with water at a level of 424 l/acre.Investigation two days after treatment revealed that the density ofaphids is reduced to less than 1/10 the density before treatment in eachcase.

EXAMPLE 3

A piece of plywood board (15 cm × 15 cm) was applied with a 200-folddilute solution of each of the emulsifiable concentrates obtained inFormulations 1 and 2 diluted with water in an amount of 50 ml/m²followed by being dried. The adult german cockroaches (Blatuellagermanica Linne) were then brought into contact with the plywood boardthus treated for 1 hour, and it was found that more than 80% cockroacheswas killed three days after contacting with the board.

EXAMPLE 4

A field of egg-plant (ripe plant) growing a number of larvae of potatolady beetle (Epilachna sparsa orientalis Dieke) was atomized with a200-fold dilute solution of each of the emulsifiable concentratesobtained in Formulation 1 in an amount of 424 l/acre. Investigation onknock-down thirty minutes after the treatment revealed that 90% larvaefell to the ground. A further investigation on density of larvae 24hours after the treatment revealed that almost 100% larvae had beencontrolled as compared with the density of larvae before the treatment.

EXAMPLE 5

Fourty-five day-old rice plants after seeding were grown in Wagner pots(1/50000) and sprayed with a 400-fold dilute solution of each of thewettable powders obtained in Formulation 8 in an amount of 10 ml/pot.The pots were then covered with a cylindrical metal net and about 20larvae of leaf hopper (Cicadula sexnotata) were released therein. Ineach case, more than 80% larvae were found to be killed one day afterthe release.

EXAMPLE 6

Each of the dusts obtained in Formulation 12 was placed uniformly at thebottom of glass trays having a diameter of 14 cm and a high side-wall inan amount of 2 g/m² and butter was applied to the glass wall except forabout 1 cm portion of the bottom. 10 adult german cockroaches per groupwere then released in the glass trays and, after contacting 30 minutes,the larvae were transferred to a fresh glass container. In each case,more than 80% of the larvae was found to be killed three days after thetreatment.

EXAMPLE 7

Each of the oil preparations obtained in Formulation 5 was atomizedusing Campel's turn table apparatus [Soap and Sanitary Chemicals, Vol.14, No. 6, 119 (1938)]in an amount of 5 ml. 20 seconds after atomizing,the shutter was opened and 100 adult oriental house flies (Muscadomestica vicina Maguant) per group were exposed to the falling atomizedfumes for a period of 10 minutes. The flies thus treated were then fedand followed by allowing to stand. More than 80% of the flies were foundto be killed in each case.

EXAMPLE 8

Each of the oil preparations obtained in Formulation 7 was sprayed in a(70 cm)³ volume glass box containing about 50 adult oriental house fliesin an amount of 0.7 ml under a pressure of 1.5 Kg/cm² and it was foundthat more than 80% of the flies was knocked down in 10 minutes after thetreatment in each case.

EXAMPLE 9

About 50 adult mosquitoes (Culex pipiens) per group were released in a(70 cm)³ volume glass box and sprayed with each of the oil preparationsobtained in Formulation 6 in an amount of 0.7 ml under a pressure of 1.5Kg/cm². It was found that more than 80% of the flies was knocked down in10 minutes after the treatment in each case.

EXAMPLE 10

A nylon net of about 15 mesh was sprayed on the lower part of a glasscylinder having a diameter of 20 cm and a height of 20 cm and butter wasapplied on the upper part of the glass cylinder in a width of about 3cm. Then 20 adult german cockroaches were released therein. The glasscylinder containing the cockroaches was plied on another glass cylinderof the same size, and further another glass cylinder having a diameterof 20 cm and a height of 40 cm was placed thereon. 0.5 ml of each of theoil preparations obtained in Formulation 7 was sprayed from the uppercylinder using a glass atomizer under a pressure of 0.75 Kg/cm² and thensealed followed by allowing to stand. It was found that more than 90% ofthe cockroaches were knocked down in 30 minutes after the treatment andthat more than 90% of the cockroaches were killed 3 days after thetreatment.

EXAMPLE 11

Insecticidal activity of each of the aerosols obtained in Formulation 10on oriental house flies was tested by an aerosol test method using aPeet grady chamber [a method reported in Soap and Chemical SpecialitiesBluebook (1965)]. The test results revealed that knock-down of more than80% of the flies was observed in 15 minutes after the treatment and morethan 70% of the flies was killed one day after the treatment in eachcase.

EXAMPLE 12

About 50 adult mosquitoes (Culex pipiens) were released in a (70 cm)³volume glass box and a mosquito coil both ends thereof having beenignited, was placed in the center of the box bottom. After 20 minutesmore than 80% of the flies was found to be knocked down.

EXAMPLE 13

About 50 adult mosquitoes (Culex pipiens) were released in a (70 cm)³volume glass box and a heating mat obtained in Formulation 11 fixed onan electrothermic plate was placed in the glass box followed by heatingto smoke. Within 20 minutes, more than 90% of the mosquitoes was foundto be knocked down.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A substituted acetate compound of the formula##STR769## wherein Y is selected from the group consisting of theformulae: ##STR770## in which R₁ and R₂ are individually hydrogen,halogen, cyano, nitro, lower alkyl, lower alkenyl, lower alkynyl, loweralkoxy, lower alkoxyalkyl, halogen-substituted lower alkyl,halogen-substituted lower alkenyl, halogen-substituted lower alkynyl,lower alkylthio, lower alkylsulfoxyl, C₂ -C₄ alkanoyl, C₂ alkanoyloxy,lower alkoxycarbonyl, lower alkenyloxycarbonyl, loweralkynyloxy-carbonyl, methylenedioxy, tetramethylene or trimethylenegroup; R₃ and R₄ are individually hydrogen, halogen, cyano, nitro, loweralkyl, lower alkenyl, lower alkynyl, lower alkoxy, lower alkoxyalkyl,halogen-substituted lower alkyl, halogen-substituted lower alkenyl,halogen-substituted lower alkynyl, lower alkylthio, lower alkylsulfoxyl,C₂ -C₄ alkanoyl, lower alkoxycarbonyl, lower alkenyloxycarbonyl or loweralkynyloxycarbonyl group; A represents an oxygen atom or a sulfur atom;R₅ represents hydrogen, halogen, cyano, nitro or lower alkyl group; m isan integer of from 1 to 3; R₆ represents hydrogen, halogen, cyano, nitroor lower alkyl group; n is an integer of from 1 to 3; and the dottedline in the formula (V) represents a double bond present at a positionconjugated or non-conjugated with the ketone (C=O), or Y represents asubstituted ethylene group of the formula (VI) ##STR771## in which R₇,R₈ and R₉ constitutes a plane together with the double bond at β-γposition of the ester group, and are individually hydrogen, lower alkyl,lower alkenyl, lower alkynyl, or halogen; Z represents a straight orbranched lower alkyl, lower alkenyl, lower alkynyl, lower alkoxy, cyano,halogen-substituted lower alkyl, halogen-substituted lower alkenyl groupor an alicyclic group having 3 to 7 carbon atoms; R₁₃ representsphthalimide, thiophthalimide, di- or tetrahydrophthalimide ordialkylmaleimide.
 2. A compound of the formula ##STR772## wherein R₁ isa member selected from the group consisting of hydrogen, methoxy,ethoxy, acetoxy, methylsulfinyl, C₁ -C₄ alkyl, trifluoromethyl, allyl,acetyl, ethoxycarbonyl, methylenedioxy, methylthio, trimethylene,tetramethylene, chlorine, fluorine, iodine, isopropenyl, propargyl,methoxymethyl, ethoxymethyl, chloroethylene, chloroallyl, butyryl,butylthio, allyloxycarbonyl, nitro and methoxycarbonyl; R₂ is a memberselected from the group consisting of hydrogen, methyl, methoxy,chlorine and bromine; R₃ is hydrogen or methyl; Z is a member selectedfrom the group consisting of C₁ -C₄ alkyl, ethoxy, allyl, bromoethyl,cyclohexyl, cyclopropylmethyl, isopropenyl, propargyl, trifluoromethyland cyano; and X is a member selected from the group consisting of:##STR773## ##STR774## ##STR775##
 3. A compound of the formula;##STR776## wherein R₅ is hydrogen or methyl; m is an integer of 1 or 2;Z is a member selected from the group consisting of methyl, propyl,allyl and propargyl; X is ##STR777##
 4. A insecticidal and miticidalcomposition comprising an insecticidally and miticidally effectiveamount of at least one substituted acetate compound as defined in claim1 and in an inert carrier.
 5. A insecticidal and miticidal compositioncontaining an insecticidally and miticidally effective amount of atleast one substituted acetate compound as defined in claim 1 in the formof an emulsifiable concentrate, a wettable powder, a dust, a granule, acoating liquid, an oil preparation, an aerosol or a mosquito coil.
 6. Amethod for controlling insects of the Order Coleoptera, Lepidoptera,Diptera, Othoptera, Hemiptera, Homoptera and Acarus by applying aninsecticidally effective amount of at least one substituted acetatecompound as defined in claim 1 to their habitats.